Method and system for ammoximation of carbonyl compounds

Abstract

Disclosed in the present invention are a method and system for the ammoximation of carbonyl compounds. The method comprises: (1) bringing a reactant stream containing a carbonyl compound, ammonia and hydrogen peroxide into contact with a catalyst to perform an ammoximation reaction, so as to obtain a product stream; (2) mixing the product stream with an organic solvent, and then simultaneously performing extraction and filtration under perturbation conditions, so as to obtain wastewater and a mixture stream; and (3) separating the mixture stream to obtain an oxime-containing organic phase and a catalyst-containing aqueous phase, and returning the catalyst-containing aqueous phase to step (1) to supply at least part of the catalyst. By means of the method and system for the ammoximation of carbonyl compounds provided by the present invention, on the premise of achieving a high conversion rate of carbonyl compounds and a high oxime selectivity, continuous and efficient separation of wastewater, a catalyst and reaction products can be achieved, the consumption of the catalyst can be reduced, and the operational stability of a device can be improved.

Description

Ammonoxime methods and systems for carbonyl compounds Technical Field

[0001] This invention relates to the field of ammoniation reaction technology, and more specifically to a method and system for the ammoniation of carbonyl compounds. Background Technology

[0002] Carbonyl compounds refer to compounds containing the >C=O functional group, such as aldehydes and ketones. The reaction of carbonyl compounds with hydroxylamine is the main method for synthesizing the corresponding oxime compounds. Taking the synthesis of cyclohexanone oxime as an example, cyclohexanone oxime is a key intermediate in the production of caprolactam, an important organic chemical raw material mainly used as a monomer for nylon-6 synthetic fibers and engineering plastics. Industrially, 98% of caprolactam is produced via the cyclohexanone oxime route. The traditional production processes for cyclohexanone oxime mainly include the hydroxylamine sulfate method (HSO), the nitrogen oxide reduction method (NO), and the hydroxylamine phosphate method (HPO). All three methods produce cyclohexanone oxime through the reaction of cyclohexanone with a salt of hydroxylamine. The preparation of different hydroxylamine salts involves first burning ammonia to produce nitrogen oxides or their salts, followed by reduction (such as hydrogenation). This process is not only lengthy, complex, and demanding, requiring stringent conditions and high equipment investment, but also generates or uses NO. X and / or SO X This leads to serious corrosion and pollution problems.

[0003] The one-step ammoximation reaction of carbonyl compounds with ammonia and hydrogen peroxide to prepare oximes is a green chemical reaction. Currently, newly built industrial production facilities all adopt the ammoximation process of cyclohexanone to prepare cyclohexanone oximes. This process uses titanium silicate molecular sieve catalysts, tert-butanol as solvent, and cyclohexanone, ammonia, and hydrogen peroxide as raw materials to prepare cyclohexanone oximes with high selectivity in one step. It not only has mild reaction conditions and high yield of target products, but also has advantages such as simple process, low equipment investment, low emissions of waste, and environmental friendliness.

[0004] tert-Butanol, used as a solvent in the ammonoximation reaction, needs to be recycled, and steam consumption occurs during distillation to recover it. In recent years, research on ammonoximation processes that do not use tert-butanol as a solvent has been increasing in order to reduce energy consumption.

[0005] CN105837468A discloses a method for preparing cyclohexanone oxime. The method uses an aqueous solution containing a small amount of inert organic solvent as the solvent, and cyclohexanone, ammonia, and hydrogen peroxide undergo an ammonoximation reaction in the solvent in the presence of an oximation catalyst. The ammonoximation reaction product is separated into an organic phase and an aqueous phase in a hydrocyclone separator and / or decanter. The oximation catalyst is separated from the aqueous phase in a decanter, membrane filter, or other equipment. This method involves high operating loads on the separation equipment and is difficult to control.

[0006] CN114436889A discloses an integrated method and apparatus for ammonia oximation reaction and separation, comprising the following steps: (1) under the condition of titanium silicate molecular sieve as catalyst, ketone, hydrogen peroxide and ammonia react to generate oxime; (2) the reactants are separated into a clear liquid containing water and oxime by cross-flow filtration; (3) the material after separation of the clear liquid is partially entered into a mixed extraction before being recycled back to the reactor, and an inert alkane solvent is added for extraction, and the resulting organic phase is an oxime solution; (4) the aqueous phase turbid liquid containing catalyst after extraction is returned to the ammonia oximation system. This method adopts a process of filtration followed by extraction and phase separation. The filtration system is unstable, the filtration equipment is prone to clogging, affecting normal production; moreover, the high oxime content in the clear liquid increases the difficulty of subsequent processing and easily causes oxime loss. Summary of the Invention

[0007] The purpose of this invention is to overcome one or more problems existing in the prior art, such as high energy consumption for product separation in ammonium oxime reaction, easy loss of oxime, unstable system operation, and high catalyst consumption, and to provide an ammonium oxime method and system for carbonyl compounds, which has the characteristics of high carbonyl compound conversion and oxime selectivity, good product separation effect, low catalyst consumption, and good operational stability.

[0008] To achieve the above objectives, a first aspect of the present invention provides a method for the ammonoximation of a carbonyl compound, the method comprising:

[0009] (1) The reactant stream containing carbonyl compound, ammonia and hydrogen peroxide is contacted with a catalyst to carry out an ammonium oxime reaction to obtain the product stream;

[0010] (2) The product stream is mixed with an organic solvent, and then extracted and filtered simultaneously under disturbed conditions to obtain wastewater and a mixture stream;

[0011] (3) The mixture stream is separated to obtain an oxime-containing organic phase and a catalyst-containing aqueous phase, and the catalyst-containing aqueous phase is returned to step (1) to provide at least a portion of the catalyst.

[0012] A second aspect of the present invention provides an ammonium oxime system for carbonyl compounds, the system comprising a carbonyl compound supply unit, an ammonia supply unit, a hydrogen peroxide supply unit, an organic solvent supply unit, an ammonium oxime reaction unit, an extraction separator, and a catalyst separator;

[0013] The ammonium oximation reaction unit includes at least one reactor for contacting carbonyl compounds, ammonia, and hydrogen peroxide from the carbonyl compound supply unit, the ammonia supply unit, and the hydrogen peroxide supply unit with a catalyst to carry out an ammonium oximation reaction, thereby obtaining a product stream.

[0014] The outlet of the ammonium oxime reaction unit is connected to the inlet of the extraction separator through a mixing pipeline. The extraction separator is equipped with a filter, a wastewater outlet, and a mixture flow outlet, which are used to simultaneously extract and filter the material from the mixing pipeline to obtain wastewater and mixture flow.

[0015] The mixing pipeline is provided with an organic solvent inlet connected to the organic solvent supply unit, which is used to mix the product stream of the ammonium oxime reaction with the organic solvent and then send it into the extraction separator.

[0016] The feed inlet of the catalyst separator is connected to the mixture outlet of the extraction separator, and is used to send the mixture stream from the extraction separator into the catalyst separator;

[0017] The catalyst separator is equipped with an organic phase outlet and an aqueous phase outlet, which are used to separate the mixture stream from the extraction separator to obtain an oxime-containing organic phase and a catalyst-containing aqueous phase. The aqueous phase outlet is connected to the ammonium oximation reaction unit through a circulation pipeline, which is used to return the catalyst-containing aqueous phase to the reactor.

[0018] The amoximation method for carbonyl compounds provided by this invention mixes the product stream of the amoximation reaction with an organic solvent. Under disturbed conditions, extraction and filtration are performed simultaneously, achieving the dual purpose of extracting reaction products and separating wastewater. The mixture stream is then separated, allowing the oxime-containing organic phase and the catalyst-containing aqueous phase to naturally separate, achieving separation of reaction products and catalyst, and catalyst recycling. Using the amoximation method and system for carbonyl compounds provided by this invention, continuous and efficient separation of wastewater, catalyst, and reaction products can be achieved while obtaining high carbonyl compound conversion rates and high oxime selectivity. The process is simple, catalyst consumption is low, significantly reducing separation load and equipment requirements, substantially lowering energy consumption and investment, and improving operational stability. Attached Figure Description

[0019] Figure 1 is a schematic diagram of a carbonyl compound ammonium oxime system according to a specific embodiment of the present invention.

[0020] Figure 2 is a schematic diagram of the carbonyl compound ammoxime system used in Comparative Example 1 according to the prior art.

[0021] Figure 3 is a schematic diagram of the carbonyl compound ammoxime system used in Comparative Example 2 according to the prior art.

[0022] Figure Label Explanation: 1. Carbonyl Compound Supply Unit; 2. Ammonia Supply Unit; 3. Hydrogen Peroxide Supply Unit; 4. Organic Solvent Supply Unit; 5. Ammonium Oximation Reaction Unit; 6. Extraction Separator; 7. Filter; 8. Catalyst Separator; 9. Filter Tank; 10. Extractor. Detailed Implementation

[0023] The specific embodiments of this application will be described in detail below. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this application.

[0024] Any specific numerical values ​​disclosed herein (including the endpoints of numerical ranges) are not limited to their exact values, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values ​​themselves; these new numerical ranges should also be considered as specifically disclosed herein.

[0025] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0026] The expressions “comprising” or “including” in this document should be interpreted as including all specifically mentioned features as well as optional, additional, or unspecified features. As used herein, the use of the term “comprising” also discloses schemes in which no other features besides the specifically mentioned features are present, such as expressions “consistently composed of” and “composed of”.

[0027] For the purposes of this invention, the term "disturbance conditions" refers to conditions that enable a mixture, such as two or more phases, to be in full contact under non-static conditions, including but not limited to stirring, oscillation, shaking, airflow agitation, ultrasonic treatment, etc.

[0028] For the purposes of this invention, the term "insoluble or slightly soluble in water" refers to an organic solvent that has a solubility in water of less than 5 g / L at room temperature (25°C) and normal pressure (1 atm), and more preferably less than 1 g / L.

[0029] The first aspect of this invention provides a method for the ammonoximeation of a carbonyl compound, the method comprising:

[0030] (1) The reactant stream containing carbonyl compound, ammonia and hydrogen peroxide is contacted with a catalyst to carry out an ammonium oxime reaction to obtain the product stream;

[0031] (2) The product stream is mixed with an organic solvent, and then extracted and filtered simultaneously under disturbed conditions to obtain wastewater and a mixture stream;

[0032] (3) The mixture stream is separated to obtain an oxime-containing organic phase and a catalyst-containing aqueous phase, and the catalyst-containing aqueous phase is returned to step (1) to provide at least a portion of the catalyst.

[0033] According to the ammoximation method for carbonyl compounds of the present invention, the product stream of the ammoximation reaction of carbonyl compounds is mixed with an organic solvent. Under disturbed conditions, extraction and filtration are performed simultaneously, thereby achieving the dual effects of extracting reaction products and separating wastewater. The oxime-containing organic phase in the mixture stream is then separated from the catalyst-containing aqueous phase, achieving separation of reaction products and catalyst, and catalyst recycling. Using the ammoximation method for carbonyl compounds provided by the present invention, continuous and efficient separation of wastewater, catalyst, and reaction products can be achieved while obtaining high carbonyl compound conversion rates and high oxime selectivity. The process is simple, catalyst consumption is low, significantly reducing separation load and equipment requirements, substantially reducing energy consumption and investment in the equipment, and improving the stability of equipment operation.

[0034] According to the present invention, the ammonoximation method can be applied to the preparation of corresponding oxime compounds from any conventional carbonyl compound in the art.

[0035] According to the present invention, the scheme of reducing separation load and separation equipment, reducing device energy consumption and improving device operation stability by simultaneous extraction and filtration can also be used in other reaction-separation integrated systems involving liquid-liquid-solid or gas-liquid-liquid-solid reactions other than the ammoniation reaction system of carbonyl compounds.

[0036] Preferably, no additional organic solvent is introduced in the ammonium oxime reaction in step (1). The organic solvent can be any organic solvent commonly used in the art, such as tert-butanol.

[0037] According to some preferred embodiments of the present invention, the carbonyl compound is selected from C3-C4. 10 Aliphatic ketones, C5-C 10 Alicyclic ketones, C6-C 10 Aromatic ketones, C5-C 10 Alicyclic aldehydes, C6-C 10 At least one of aromatic aldehydes. Preferably, the carbonyl compound is selected from at least one of cyclohexanone, acetone, methyl ethyl ketone, cyclopentanone, acetophenone, p-hydroxyacetophenone, furfural, benzaldehyde, and p-methylbenzaldehyde.

[0038] The present invention does not impose any particular limitation on the selection of the catalyst, and any conventional ammonia oxime reaction catalyst in the art can be used. Preferably, the catalyst comprises a titanium silicate molecular sieve, wherein the titanium silicate molecular sieve is selected from at least one of TS-1, TS-2, Ti-ZSM-5, Ti-ZSM-12, Ti-ZSM-48, Ti-β, Ti-MCM-41, Ti-MOR, Ti-MWW, and Ti-SBA-15.

[0039] The present invention does not particularly limit the form of the catalyst, which can be in the form of molecular sieve powder or a shaped catalyst formed by arbitrary shaping. Those skilled in the art can choose according to actual needs.

[0040] According to some preferred embodiments of the present invention, the reaction stream in step (1) further comprises a liquid silicon-containing additive. Using the above preferred embodiments helps to further suppress the dissolution of silicon in the catalyst, reduce catalyst deactivation, and further improve the stability of the reaction.

[0041] The liquid silicon-containing additive can be in liquid form such as sol, solution, suspension, or emulsion. The silicon-containing additive can be an inorganic silicon-containing substance and / or an organic silicon-containing substance.

[0042] Preferably, the inorganic silicon-containing material is silicon oxide and / or silicate, and the silicate can be sodium silicate, potassium silicate, aluminum silicate, etc.

[0043] Preferably, the organic silicon-containing substance is a silicate ester and / or a silane, and the silicate ester may be ethyl silicate.

[0044] According to some preferred embodiments of the present invention, the amount of liquid silicon-containing additive used is such that the silicon concentration in the reaction stream is 0.1-10000 ppm. Preferably, the amount added is such that the silicon content in the reaction stream reaches its dissolution equilibrium concentration. Those skilled in the art will understand that, due to differences in the composition of the reaction system, the equilibrium concentration of silicon in the system will vary, and those skilled in the art can add an appropriate amount of silicon-containing additive according to actual needs. Preferably, the amount of liquid silicon-containing additive used is such that the silicon concentration in the reaction stream is 30-3000 ppm.

[0045] According to some preferred embodiments of the present invention, in step (1), the molar ratio of the carbonyl compound, hydrogen peroxide and ammonia is 1:(1-2):(1-3), preferably 1:(1-1.5):(1-2).

[0046] According to some preferred embodiments of the present invention, the hydrogen peroxide is provided by hydrogen peroxide solution, wherein the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 10-80%, preferably 20-70%.

[0047] According to some preferred embodiments of the present invention, in step (3), the mass fraction of the catalyst in the catalyst-containing aqueous phase returned to step (1) is 0.5-15%, for example, it can be a specific and non-limiting mass fraction such as 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or any range between the two. Preferably, the mass fraction of the catalyst in the catalyst-containing aqueous phase returned to step (1) is 2-10%.

[0048] According to some preferred embodiments of the present invention, in step (1), the temperature of the ammonium oxime reaction is 50-100°C, for example, it can be a specific but not limiting temperature such as 50°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, or any range between the two, preferably 60-95°C.

[0049] According to some preferred embodiments of the present invention, in step (1), the pressure of the ammonium oxime reaction is 0-1 MPa, for example, it can be a specific but not limiting pressure or any range between two such pressures, such as 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1 MPa, etc., preferably 0.1-0.6 MPa. In the present invention, unless otherwise specified, all pressures mentioned refer to gauge pressure.

[0050] According to the present invention, in step (2), the product stream is mixed with an organic solvent, and the oxime is extracted into the organic phase to form a mixture stream containing an organic phase, an aqueous phase and a catalyst.

[0051] The present invention has a wide range of choices for the organic solvents used in step (2), and conventional organic solvents that are insoluble or slightly soluble in water can be used in the present invention. Preferably, the organic solvent is selected from C6-C. 12 Alkanes, C5-C 11 Cycloalkanes, C6-C 10 At least one of aromatic hydrocarbons and C6-C8 alcohols, such as n-hexane, cyclohexane, benzene, toluene, isohepyl alcohol, isooctyl alcohol, etc.

[0052] According to some preferred embodiments of the present invention, the mass ratio of the organic solvent to the oxime in the product stream is (1-10):1, for example, it can be a specific but not limiting mass ratio such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or any range between the two. Preferably, the mass ratio of the organic solvent to the oxime in the product stream is (1-6):1.

[0053] According to the present invention, in step (2), "simultaneous extraction and filtration" means that extraction and filtration are carried out in the same process, such as extraction and filtration are carried out in the same device, so as to achieve synchronous operation of extraction and filtration.

[0054] According to the present invention, in step (2), after the product stream is mixed with the organic solvent, it is filtered during the extraction process. The mixed stream is disturbed, which not only achieves efficient extraction, but also allows for selective separation of water by further optimizing the conditions of simultaneous extraction and filtration. That is, only a portion of the aqueous phase passes through the filter, while the organic phase and the remaining aqueous phase containing the catalyst are retained, thereby achieving efficient separation of the aqueous phase. Moreover, this method has a low filtration load, low energy consumption, low catalyst loss, and minimal oxime loss. By controlling the amount of wastewater filtered out to introduce water into the system, including the amount of water generated in the reaction, the amount of water brought in by hydrogen peroxide, and possibly the amount of aqueous solution in the liquid silicon-containing additive, it is beneficial to maintain the water balance of the system.

[0055] According to some preferred embodiments of the present invention, the volume ratio of the aqueous phase in the product stream to the sum of the volumes of the organic solvent and the organic phase in the product stream is greater than 1:1. For example, it can be a specific, but not limiting, volume ratio or any range between the two, such as 1.05:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 15:1, etc., preferably greater than or equal to 1.05:1. The inventors have discovered that in an extraction separator, the volume ratio of the aqueous phase to the organic phase significantly affects the amount of organic phase in the filtered liquid. When this volume ratio is controlled at 1:1, the filtered liquid contains approximately 3% organic phase; when this volume ratio is controlled at 1.05:1, the filtered liquid is an aqueous phase. Therefore, by optimizing the volume ratio of the aqueous phase to the organic phase in the extraction separator, selective separation of water can be achieved, i.e., only a portion of the aqueous phase passes through the filter, while the organic phase and the remaining aqueous phase containing the catalyst are retained, further reducing oxime loss.

[0056] According to some preferred embodiments of the present invention, the amount of wastewater filtered out is controlled to be 2-25 wt%, preferably 3-20 wt%, based on the mass of the aqueous phase in the product stream.

[0057] Without being bound by any particular theory, it is understood that in the above process, most of the oxime products dissolve in the organic solvent, and the aqueous phase serves as the raffinate phase. The oxime content in this aqueous phase is significantly reduced, which helps to lower the difficulty of subsequent wastewater treatment, greatly reduce oxime loss, and improve the stability of the equipment operation. The filtered aqueous phase can be recycled as wastewater, for example, by further recovering ammonia and a small amount of oxime, followed by biochemical treatment. Those skilled in the art can choose according to actual needs; this invention does not have special requirements in this regard, as long as wastewater discharge standards are met.

[0058] According to some preferred embodiments of the present invention, in step (2), the mass fraction of oxime in the wastewater is 0.01-3%, preferably 0.01-2%.

[0059] According to some preferred embodiments of the present invention, in step (2), the extraction temperature is 20-90°C, preferably 40-80°C.

[0060] According to some preferred embodiments of the present invention, the filtration accuracy in step (2) is 0.01-50 μm, preferably 2-30 μm.

[0061] According to the present invention, the extraction and filtration in step (2) can be carried out using a device that can simultaneously extract and filter and separate a portion of water from a liquid-liquid-solid or gas-liquid-liquid-solid multiphase system.

[0062] According to some preferred embodiments of the present invention, the extraction and filtration in step (2) are carried out in an extraction separator, and the extraction separator is provided with a filter.

[0063] According to some preferred embodiments of the present invention, the filter material is hydrophilic. Preferably, the filter material is ceramic or metal, more preferably metal. Preferably, the metal can be oxidized, such as by ultraviolet-ozone or plasma treatment.

[0064] According to the present invention, in step (3), the mixture stream obtained by simultaneous extraction and filtration is separated to obtain an oxime-containing organic phase and a catalyst-containing aqueous phase. The oxime-containing organic phase does not contain the catalyst, which is dispersed in the aqueous phase. Due to the large density difference between the organic and aqueous phases, the catalyst can be separated from the reaction products through natural phase separation. The organic phase containing the oxime and solvent can be directly or optionally separated by a solvent and then sent to the next step. The aqueous phase is a catalyst slurry, which is returned to step (1) to provide at least a portion of the catalyst.

[0065] According to some embodiments of the present invention, a slurry containing fresh catalyst may be intermittently added according to specific operating conditions (e.g., when the mass fraction of catalyst in the catalyst-containing aqueous phase returning to step (1) decreases below the lower limit due to catalyst loss during long-term operation of the system). The slurry containing fresh catalyst is a slurry containing fresh catalyst prepared with water.

[0066] According to some preferred embodiments of the present invention, the separation in step (3) is carried out in a catalyst separator, wherein the aqueous phase section of the catalyst separator is provided with a stirrer for stirring the aqueous phase containing the catalyst.

[0067] The agitator in the aqueous phase section of the catalyst separator is designed to prevent catalyst deposition in the separator and avoid back-mixing of the organic and aqueous phases, ensuring continuous and stable separation of the two phases and catalyst circulation. Therefore, efficient separation of catalyst and reaction products can be achieved without the need for separation equipment such as hydrocyclones, decanters, and membrane filters, reducing material loss.

[0068] The present invention does not have special requirements for the rotation speed of the stirrer. Those skilled in the art can select it according to different equipment sizes, stirrer types, stirring blade diameters, etc., as long as it can prevent the catalyst from depositing in the catalyst separator and avoid back mixing of the organic phase and the aqueous phase.

[0069] Preferably, the catalyst separator is provided with a gas phase outlet at the top for discharging non-condensable gases (such as ammonia, gaseous products generated by the reaction) from the catalyst separator.

[0070] According to some preferred embodiments of the present invention, in step (1), the carbonyl compound and the aqueous phase containing the catalyst returned from step (1) are mixed, and then contacted with ammonia, hydrogen peroxide, and the catalyst. Preferably, for example, the feed ratio of the carbonyl compound and the aqueous phase containing the catalyst returned from step (1) is 1:5-50 by mass, for example, it can be a specific but not limiting feed ratio or any range between the two, such as 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, etc. Using the above preferred embodiments is beneficial for extending the service life of the catalyst and reducing catalyst consumption.

[0071] A second aspect of the present invention provides an ammonium oxime system for carbonyl compounds. As shown in FIG1, the system includes a carbonyl compound supply unit 1, an ammonia supply unit 2, a hydrogen peroxide supply unit 3, an organic solvent supply unit 4, an ammonium oxime reaction unit 5, an extraction separator 6, and a catalyst separator 8;

[0072] The ammonium oximation reaction unit 5 includes at least one reactor for contacting carbonyl compounds, ammonia and hydrogen peroxide from carbonyl compound supply unit 1, ammonia supply unit 2 and hydrogen peroxide supply unit 3 with a catalyst to carry out an ammonium oximation reaction to obtain a product stream.

[0073] The outlet of the ammonium oxime reaction unit 5 is connected to the inlet of the extraction separator through a mixing pipeline. The extraction separator is equipped with a filter, a wastewater outlet and a mixture flow outlet, which are used to simultaneously extract and filter the material from the mixing pipeline to obtain wastewater and mixture flow.

[0074] The mixing pipeline is provided with an organic solvent inlet connected to the organic solvent supply unit 4, which is used to mix the product stream of the ammonium oxime reaction with the organic solvent and then send it into the extraction separator 6.

[0075] The feed inlet of the catalyst separator 8 is connected to the mixture outlet of the extraction separator 6, and is used to feed the mixture from the extraction separator 6 into the catalyst separator 8.

[0076] The catalyst separator 8 is provided with an organic phase outlet and an aqueous phase outlet, which are used to separate the mixed stream from the extraction separator 6 to obtain an oxime-containing organic phase and a catalyst-containing aqueous phase. The aqueous phase outlet is connected to the ammonium oximation reaction unit 5 through a circulation pipeline, which is used to return the catalyst-containing aqueous phase to the reactor.

[0077] The present invention does not impose a particular limitation on the number of reactors in the ammonium oximation reaction unit. Those skilled in the art can select and set one or more reactors according to actual production needs, and two or more reactors can be connected in series and / or in parallel. Preferably, the ammonium oximation reaction unit includes 1-4 reactors, for example 1-2 reactors.

[0078] The present invention does not particularly limit the type of reactor, but preferably, the reactor is a stirred tank reactor.

[0079] According to the present invention, when multiple reactors are connected in series and / or in parallel, preferably each reactor is independently connected to a hydrogen peroxide supply unit so that hydrogen peroxide is fed simultaneously by multiple supply units.

[0080] According to some preferred embodiments of the present invention, the system further includes an additive supply unit for supplying a silicon-containing additive to the ammonium oxime reaction unit.

[0081] According to some preferred embodiments of the present invention, in the extraction separator, the filter is made of ceramic or metal, preferably metal.

[0082] Preferably, the filtration accuracy of the filter is 0.01-50μm, and more preferably 2-30μm.

[0083] According to some embodiments of the present invention, the aqueous phase section of the catalyst separator is equipped with a stirrer for stirring the aqueous phase containing the catalyst. The stirrer is configured to prevent catalyst deposition in the catalyst separator and to avoid backmixing of the organic phase and the aqueous phase. Therefore, efficient separation of the catalyst and reaction products can be achieved without the need for separation equipment such as hydrocyclones, decanters, and membrane filters, reducing material loss.

[0084] According to some preferred embodiments of the present invention, the catalyst separator is provided with a gas phase outlet at the top for discharging non-condensable gases (such as ammonia, gaseous products generated by the reaction) from the catalyst separator.

[0085] According to some preferred embodiments of the present invention, the catalyst separator includes a vessel body and a stirrer, an inner extension tube, and an inner sleeve disposed within the vessel body. The inner sleeve is fitted inside the inner extension tube and is used to convey the mixture flow to the inner extension tube. The inner extension tube is used to convey the mixture flow to the vessel body for two-phase separation to obtain an organic phase and an aqueous phase. A gas phase balance port is provided on the side wall of the inner extension tube to maintain the gas phase balance of the vessel body. The stirrer is disposed within the aqueous phase portion of the vessel body and is used to stir the aqueous phase.

[0086] According to the present invention, in the catalyst separator, the combination of the inner extension tube and the inner sleeve can reduce the amount of catalyst carried in the organic phase; the stirrer can prevent catalyst deposition in the vessel body, while ensuring the separation of the organic and water phases, avoiding back-mixing, and achieving continuous and stable catalyst circulation. In this invention, there is no particular limitation on the installation position of the inner extension tube. Preferably, the top end of the inner extension tube is located outside the vessel body, and the bottom end of the inner extension tube is located inside the vessel body. By positioning the bottom end of the inner extension tube inside the vessel body, the mixture stream from the extraction separator can be transported to the vessel body for two-phase separation.

[0087] In some embodiments of the present invention, preferably, the top end of the inner sleeve is flush with the top end of the inner extension tube, and the top of the annular space formed by the inner sleeve and the inner extension tube is closed.

[0088] In this invention, the rotational speed of the agitator is not particularly limited. The rotational speed is related to the selection of the agitator blade, the ratio of the blade diameter to the inner diameter of the vessel, etc. Those skilled in the art can adjust it according to the actual device structure, as long as it can prevent solid materials from depositing in the vessel and avoid back mixing of the organic and aqueous phases. For example, the agitator rotational speed can be 5-200 rpm.

[0089] According to some preferred embodiments of the present invention, the bottom end of the stirrer is provided with a stirring paddle.

[0090] In this invention, the specific type of stirring paddle is not particularly limited; any stirring device capable of preventing solid materials from depositing in the vessel is applicable. Preferably, the stirring paddle is selected from at least one of propeller-type stirring paddles, turbine-type stirring paddles, anchor-type stirring paddles, and frame-type stirring paddles.

[0091] According to some preferred embodiments of the present invention, the number of layers of the stirring paddle is 1-3.

[0092] According to some preferred embodiments of the present invention, an anti-surge baffle is provided at the bottom end of the inner tube. The anti-surge baffle is used to buffer the mixture flow from the extraction separator.

[0093] According to some preferred embodiments of the present invention, an overflow weir is provided at the upper part of the vessel. The overflow weir is used to overflow the organic phase to obtain the organic phase product.

[0094] According to some preferred embodiments of the present invention, an organic phase outlet is provided at the upper part of the vessel body, and the organic phase outlet is connected to the overflow weir.

[0095] According to some preferred embodiments of the present invention, the bottom of the vessel is provided with a water phase outlet.

[0096] According to some preferred embodiments of the present invention, a gas phase outlet is provided at the top of the vessel.

[0097] According to some preferred embodiments of the present invention, the gas phase balance port is directly connected to the gas phase space above the vessel body, or the gas phase balance port is connected to the gas phase space above the vessel body through a pipeline.

[0098] According to some preferred embodiments of the present invention, the carbonyl compound supply unit is connected to the circulation pipeline for mixing the carbonyl compound with the catalyst-containing aqueous phase from the catalyst separator and then feeding it into the reactor. According to the present invention, the above-mentioned devices are connected via a material flow pipeline, which may or may not be equipped with a transfer pump. According to some embodiments of the present invention, no transfer pump is provided on the connecting pipeline between the ammonium oxime reaction unit and the extraction separator, or between the extraction separator and the catalyst separator; overflow is used for material discharge and feeding. According to some embodiments of the present invention, a transfer pump is provided on the circulation pipeline connecting the aqueous phase outlet of the catalyst separator to the ammonium oxime reaction unit to control the circulation of the catalyst-containing aqueous phase from the catalyst separator.

[0099] In some embodiments of the present invention, the ammonium oxime system of the carbonyl compound according to the second aspect is a system for carrying out the ammonium oxime method of the carbonyl compound according to the first aspect.

[0100] According to some preferred embodiments of the present invention, the above-described system is used for the ammonium oximation reaction of carbonyl compounds, specifically comprising: feeding a carbonyl compound, ammonia, hydrogen peroxide, and a catalyst into an ammonium oximation reaction unit to carry out the ammonium oximation reaction and obtain a product stream; mixing the product stream from the outlet of the ammonium oximation reaction unit with an organic solvent in a mixing pipeline, and then feeding it into an extraction separator, wherein the extraction separator is equipped with a filter and a stirrer; under disturbed conditions, a portion of the aqueous phase is controlled to be separated by the filter and discharged from the system through a wastewater outlet; the mixture stream is fed into a catalyst separator through a mixture stream outlet. The mixture stream is separated into an aqueous phase and an organic phase in the catalyst separator; the aqueous phase section of the catalyst separator is equipped with a stirrer for stirring the aqueous phase containing the catalyst; the aqueous phase containing the catalyst is returned to the ammonium oximation reaction unit, and the organic phase containing oxime is fed into the next process.

[0101] The present invention discloses the following embodiments:

[0102] Option 1: A method for the ammonoximeation of a carbonyl compound, characterized in that the method comprises:

[0103] (1) The reaction system containing carbonyl compounds, ammonia and hydrogen peroxide is contacted with a catalyst to carry out an ammonium oxime reaction to obtain a mixture of products;

[0104] (2) The product mixture is mixed with an organic solvent, and then extracted and filtered simultaneously under stirring conditions to obtain wastewater and mixed liquid;

[0105] (3) Separate the mixture to obtain an oxime-containing organic phase and a catalyst-containing aqueous phase, and return the catalyst-containing aqueous phase to step (1) to provide at least a portion of the catalyst.

[0106] Option 2: The method according to Option 1, wherein the carbonyl compound is selected from C3-C4. 10 aliphatic ketones, C5-C 10 Cyclic aliphatic ketones or aromatic ketones, C5-C 10 At least one of cyclic aliphatic aldehydes or aromatic aldehydes, preferably at least one of cyclohexanone, acetone, methyl ethyl ketone, cyclopentanone, acetophenone, p-hydroxyacetophenone, furfural, benzaldehyde and p-methylbenzaldehyde;

[0107] Preferably, the catalyst comprises a titanium-silicon molecular sieve, wherein the titanium-silicon molecular sieve is selected from at least one of TS-1, TS-2, Ti-ZSM-5, Ti-ZSM-12, Ti-ZSM-48, Ti-β, Ti-MCM-41, Ti-MOR, Ti-MWW and Ti-SBA-15;

[0108] Preferably, the reaction system in step (1) further includes a liquid silicon-containing additive, wherein the liquid silicon-containing additive is selected from inorganic silicon-containing substances and / or organic silicon-containing substances;

[0109] Preferably, the inorganic silicon-containing material is silicon oxide and / or silicate, and the organic silicon-containing material is silicate ester and / or silane;

[0110] Preferably, the amount of liquid silicon-containing additive used is such that the silicon concentration in the reaction system is 0.1-10000 ppm.

[0111] Scheme 3: According to the method of Scheme 1 or 2, wherein in step (1), the molar ratio of the carbonyl compound, hydrogen peroxide and ammonia is 1:(1-2):(1-3), preferably 1:(1-1.5):(1-2);

[0112] Preferably, the hydrogen peroxide is provided by hydrogen peroxide solution, wherein the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 10-80%, preferably 20-70%;

[0113] Preferably, in step (3), the mass fraction of the catalyst in the aqueous phase containing the catalyst returned from step (1) is 0.5-15%, preferably 2-10%;

[0114] Preferably, the temperature of the ammonium oxime reaction is 50-100℃, more preferably 60-95℃, and the reaction pressure is 0-1MPa, more preferably 0.1-0.6MPa;

[0115] Preferably, no additional organic solvent is introduced in the ammonium oxime reaction described in step (1).

[0116] Option 4: The method according to any one of Options 1-3, wherein in step (2), the organic solvent is selected from organic solvents that are insoluble or slightly soluble in water, preferably C6-C. 12 Alkanes, C5-C 11 Cycloalkanes, C6-C 10 At least one of aromatic hydrocarbons and C6-C8 alcohols;

[0117] Preferably, the mass ratio of the organic solvent to the product mixture based on the carbonyl compound is (1-10):1, more preferably (1-6):1.

[0118] Scheme 5: The method described in any one of Schemes 1-4, wherein in step (2), the extraction temperature is 20-90℃, preferably 40-80℃;

[0119] Preferably, the filtration accuracy in step (2) is 0.01-50 μm, and more preferably 2-30 μm;

[0120] Preferably, in step (2), the mass fraction of oxime in the wastewater is 0.01-3%, more preferably 0.01-2%.

[0121] Scheme 6: The method according to any one of Schemes 1-5, wherein the extraction and filtration in step (2) are carried out in an extraction separator, and the extraction separator is provided with a filter;

[0122] Preferably, the filter is made of ceramic or metal, and more preferably metal;

[0123] Preferably, the separation in step (3) is carried out in a catalyst separator, wherein the aqueous phase section of the catalyst separator is equipped with a stirrer for stirring the aqueous phase.

[0124] Option 7: An ammonoximation reaction system for carbonyl compounds, characterized in that the reaction system comprises a carbonyl compound supply unit, an ammonia supply unit, a hydrogen peroxide supply unit, an organic solvent supply unit, an ammonoximation reaction unit, an extraction separator, and a catalyst separator;

[0125] The ammonium oxime reaction unit includes at least one reactor for ammonium oxime reaction of carbonyl compound, ammonia and hydrogen peroxide from carbonyl compound supply unit, ammonia supply unit and hydrogen peroxide supply unit.

[0126] The outlet of the ammonium oxime reaction unit is connected to the inlet of the extraction separator through a mixing pipeline. The extraction separator is equipped with a filter, a wastewater outlet, and a mixed liquid outlet.

[0127] The mixing pipeline is provided with an organic solvent inlet connected to the organic solvent supply unit, which is used to mix the organic solvent with the ammonium oxime reaction product and then send it into the extraction separator.

[0128] The feed inlet of the catalyst separator is connected to the mixed liquid outlet of the extraction separator, and is used to feed the mixed liquid from the extraction separator into the catalyst separator; the aqueous phase outlet of the catalyst separator is connected to the ammonium oxime reaction unit, and is used to return the aqueous phase containing the catalyst to the reactor.

[0129] Option 8: The reaction system according to Option 7, wherein the ammonium oxime reaction unit includes 1-4 reactors, preferably 1-2 reactors;

[0130] Preferably, the reactor is a stirred tank reactor;

[0131] Preferably, each reactor is independently connected to a hydrogen peroxide supply unit;

[0132] Preferably, the reaction system further includes an additive supply unit for supplying liquid silicon-containing additives to the ammonium oxime reaction unit.

[0133] Option 9: The reaction system according to Option 7 or 8, wherein the outlet of the ammonium oximation reaction unit is connected to the inlet of the extraction separator via a pipeline, and an organic solvent inlet is provided on the pipeline for mixing the product mixture from the ammonium oximation reaction unit with an organic solvent and then sending it into the extraction separator.

[0134] Preferably, in the extraction separator, the filter is made of ceramic or metal, preferably metal;

[0135] Preferably, the filtration accuracy of the filter is 0.01-50μm, and more preferably 2-30μm.

[0136] Option 10: The reaction system according to any one of Options 1-9, wherein the aqueous phase section of the catalyst separator is equipped with a stirrer for stirring the aqueous phase;

[0137] Preferably, the catalyst separator is provided with a gas phase outlet at the top.

[0138] To facilitate understanding of the present invention, the following embodiments are provided. However, these embodiments are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0139] Example

[0140] The present invention will be further described below with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

[0141] Characterization methods

[0142] Gas chromatography: An Agilent 7890B gas chromatograph equipped with a flame ionization detector (FID) was used for product analysis. The chromatographic column was an Agilent HP-INNOWax capillary column (stationary phase: polyethylene glycol, column length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm). The chromatographic conditions were as follows: injector temperature 260 °C; detector (FID) temperature 280 °C. A temperature program was used: initial column temperature 100 °C, held for 10 minutes; then increased to 230 °C at a rate of 20 °C / min and held for 20 minutes. High-purity nitrogen (N2) was used as the carrier gas at a flow rate of 1.0 mL / min. Split injection was used with a split ratio of 50:1. The injection volume was 1.0 μL. The organic phase effluent from the catalyst separator was cooled to room temperature, and a sample was taken for GC analysis. The mass percentages of carbonyl compounds, oximes, and reaction impurities were calculated using the area normalization method with correction factors. The carbonyl compound conversion, oxime selectivity, and catalyst consumption were then calculated using the following formula:

[0143] Where w% is the mass percentage of the corresponding component in the organic phase output of the catalyst separator; α is the molecular weight ratio of carbonyl compound and oxime; m (catalyst) is the total amount of catalyst added, g; F (carbonyl compound) is the carbonyl compound feed rate, kg / h; t is the unit operating time, h; when calculating catalyst consumption, the carbonyl compound conversion rate and oxime selectivity are the algebraic averages of the initial and final conversion rates and selectivities.

[0144] Unless otherwise specified, the reagents used in the following examples and comparative examples are all conventionally used in the art, and the methods employed are all conventionally used in the art.

[0145] Example 1

[0146] The system shown in Figure 1 is adopted.

[0147] Cyclohexanone, ammonia, and hydrogen peroxide are introduced into a reactor and reacted at a temperature of 89-91℃ and a pressure of 0.4MPa. The effective volume of the reactor is 300mL, and it contains 10g of TS-1 titanium-silicon molecular sieve catalyst. The feed rates are: cyclohexanone 35g / h, ammonia 8g / h, and hydrogen peroxide (35% hydrogen peroxide by mass) 40g / h. The product stream overflows from the reactor outlet, mixes with toluene, and is sent to an extraction separator at a toluene flow rate of 85g / h. A sintered metal filter with a filtration accuracy of 10-20 μm is installed in the extraction separator. The material is stirred and mixed for extraction at 50℃. The volume ratio of aqueous phase to organic phase is 4.7:1. Simultaneously, part of the aqueous phase is separated by the filter, and the filtration rate is controlled by a pump at 40.5 g / h (accounting for 6.3% of the aqueous phase mass in the product stream). The mass fraction of oxime in the filtrate is 0.98%. The filtrate is sent to the next process as wastewater. The remaining mixture overflows into the catalyst separator, where it is separated into organic and aqueous phases. The catalyst separator is equipped with a stirrer in the aqueous phase section, and the stirring speed is controlled at 130 rpm. The aqueous phase containing catalyst is circulated back to the reactor. The mass fraction of catalyst in the circulating catalyst slurry is 2.5%. The organic phase is a toluene-cyclohexanone oxime solution, which overflows into a storage tank and is sent to the next process.

[0148] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the cyclohexanone conversion rate decreased to below 99.6%, the feeding of cyclohexanone, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. The conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0149] Comparative Example 1

[0150] The system shown in Figure 2 is adopted.

[0151] Cyclohexanone, ammonia, and hydrogen peroxide are introduced into a reactor and reacted at a temperature of 89-91℃ and a pressure of 0.4MPa. The effective volume of the reactor is 300mL, and it contains 10g of TS-1 titanium-silicon molecular sieve catalyst. The feed rates are: cyclohexanone 35g / h, ammonia 8g / h, and hydrogen peroxide (35% hydrogen peroxide by mass) 40g / h. The product stream overflows from the reactor outlet into a filter tank 9 equipped with a sintered metal filter (filtration accuracy of 10-20μm) and a stirrer. The temperature of the pipeline and filter tank must be maintained above 85℃ to prevent the solidification and precipitation of cyclohexanone oxime. The volume ratio of aqueous phase to organic phase is 17.5:1. The filtration rate is controlled by a pump at 42.9g / h (accounting for 6.7% of the aqueous phase in the product stream). The oxime by mass fraction in the filtrate reaches 6.3%, and the oxime is prone to precipitation. The catalyst tends to stick to the walls, and the filtration system is unstable. The remaining stream overflows from the filter tank, mixes with toluene, and enters the extractor 10 for thorough extraction under stirring. The toluene flow rate is 85 g / h. The mixture overflows from the extractor into the catalyst separator, where it is separated into an organic phase and an aqueous phase. The catalyst separator is equipped with a stirrer in the aqueous phase section, with the stirring rate controlled at 130 rpm. The aqueous phase is a slurry containing the catalyst, which is recycled back to the reactor. The organic phase is a toluene-cyclohexanone oxime solution, which overflows into the storage tank and is sent to the next process.

[0152] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the cyclohexanone conversion rate decreased to below 99.6%, the feeding of cyclohexanone, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. Gas chromatography was used for analysis. Conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0153] Comparative Example 2

[0154] The system shown in Figure 3 is adopted.

[0155] Cyclohexanone, ammonia, and hydrogen peroxide are fed into a reactor and reacted at 89-91℃ and 0.4MPa. The effective volume of the reactor is 300mL, and it contains 10g of TS-1 titanium-silicon molecular sieve catalyst. The feed rates are: cyclohexanone 35g / h, ammonia 8g / h, and hydrogen peroxide (35% hydrogen peroxide by mass) 40g / h. The product stream overflows from the reactor outlet and mixes with toluene before entering extractor 10. Extraction is carried out under stirring at a toluene flow rate of 85g / h and an extraction temperature of 50℃. The volume ratio of the aqueous phase to the organic phase is 4.7:1. The mixture overflows from the extractor into a catalyst separator, where it separates into an organic phase and an aqueous phase. A stirrer is installed in the aqueous phase section of the catalyst separator, with a stirring speed controlled at 130rpm. The aqueous phase is a slurry containing the catalyst, and the organic phase is a toluene-cyclohexanone oxime solution. The overflow enters a storage tank and is then sent to the next process. The aqueous phase enters the filter tank 9, which is equipped with a metal sintered filter (filtration accuracy of 10-20μm) and a stirrer. The filtration rate is controlled by a pump to be 40.5g / h (accounting for 6.3% of the aqueous phase mass in the product stream). The oxime mass fraction in the filtrate is 0.98%, and the remaining stream is recycled back to the reactor.

[0156] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the cyclohexanone conversion rate decreased to below 99.6%, the feeding of cyclohexanone, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. Gas chromatography was used for analysis. Conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0157] Example 2

[0158] The system shown in Figure 1 is adopted.

[0159] Cyclohexanone, ammonia, and hydrogen peroxide are introduced into a reactor and reacted at a temperature of 89-91℃ and a pressure of 0.4MPa. The effective volume of the reactor is 300mL, and it contains 10g of TS-1 titanium-silicon molecular sieve catalyst. The feed rates are: cyclohexanone 35g / h, ammonia 8g / h, and hydrogen peroxide (35% hydrogen peroxide by mass) 40g / h. The reaction stream overflows from the reactor outlet, mixes with cyclohexane, and is sent to an extraction separator at a cyclohexane flow rate of 200g / h. A sintered metal filter with a filtration accuracy of 10-20 μm is installed in the extraction separator. The material is stirred and mixed for extraction at 60℃. The volume ratio of aqueous phase to organic phase is 2.2:1. Simultaneously, part of the aqueous phase is separated by the filter, and the pump controls the extraction rate to 40.6 g / h (accounting for 6.3% of the aqueous phase mass in the product material). The oxime mass fraction in the filtrate is 1.16%. The filtrate is sent to the next process as wastewater. The remaining mixture overflows into the catalyst separator, where it is separated into organic and aqueous phases. The catalyst separator is equipped with a stirrer in the aqueous phase section, and the stirring speed is controlled at 180 rpm. The aqueous phase containing the catalyst is recycled back to the reactor. The organic phase is a cyclohexane-cyclohexanone oxime solution, which overflows into a storage tank and is sent to the next process.

[0160] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the cyclohexanone conversion rate decreased to below 99.6%, the feeding of cyclohexanone, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. Gas chromatography was used for analysis. Conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0161] Example 3

[0162] The system shown in Figure 1 is adopted.

[0163] Methyl ethyl ketone (MEK), ammonia, and hydrogen peroxide are introduced into a reactor and reacted at a temperature of 61-63℃ and a pressure of 0.3 MPa. The effective volume of the reactor is 300 mL, and it contains 20 g of Ti-MWW titanium-silicon molecular sieve catalyst. The feed rates are: MEK 35 g / h, ammonia 12 g / h, and hydrogen peroxide (35% hydrogen peroxide by mass) 56 g / h. The product stream overflows from the reactor outlet, mixes with isooctanol, and is sent to an extraction separator at an isooctanol flow rate of 210 g / h. A sintered metal filter with a filtration accuracy of 10-20 μm is installed in the extraction separator. The material is stirred and mixed for extraction at 40℃. The volume ratio of aqueous phase to organic phase is 1.05:1. Simultaneously, part of the aqueous phase is separated by the filter, and the filtration rate is controlled by a pump at 56.6 g / h (accounting for 18.5% of the aqueous phase mass in the product material). The mass fraction of oxime in the filtrate is 1.70%. The filtrate is sent to the next process as wastewater. The remaining mixture overflows into the catalyst separator, where it is separated into organic and aqueous phases. The catalyst separator is equipped with a stirrer in the aqueous phase section, and the stirring speed is controlled at 150 rpm. The aqueous phase containing catalyst is circulated back to the reactor. The mass fraction of catalyst in the circulating catalyst slurry is 5.0%. The organic phase is an isooctanol-methyl ethyl ketone oxime solution, which overflows into a storage tank and is sent to the next process.

[0164] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the methyl ethyl ketone (MEK) conversion rate decreased to below 99.0%, the feeding of MEK, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. Gas chromatography was used for analysis. Conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0165] Example 4

[0166] The system shown in Figure 1 is adopted.

[0167] Benzaldehyde, ammonia, and hydrogen peroxide are introduced into a reactor and reacted at a temperature of 69-71℃ and a pressure of 0.2MPa. The effective volume of the reactor is 300mL, and it contains 15g of Ti-MOR catalyst. The feed rates are: benzaldehyde 35g / h, ammonia 10g / h, and hydrogen peroxide (27.5% hydrogen peroxide by mass) 49g / h. The product stream overflows from the reactor outlet, mixes with toluene, and is sent to an extraction separator at a toluene flow rate of 90g / h. A sintered metal filter with a filtration accuracy of 10-20 μm is installed in the extraction separator. The material is stirred and mixed for extraction at 40℃. The volume ratio of aqueous phase to organic phase is 2.4:1. Simultaneously, part of the aqueous phase is separated by the filter, and the pump controls the extraction rate to 49.0 g / h (accounting for 14.9% of the aqueous phase mass in the product material). The oxime mass fraction in the filtrate is 0.1%. The filtrate is sent to the next process as wastewater. The remaining mixture overflows into the catalyst separator, where it is separated into organic and aqueous phases. The catalyst separator is equipped with a stirrer in the aqueous phase section, and the stirring rate is controlled at 70 rpm. The aqueous phase containing catalyst is circulated back to the reactor. The mass fraction of catalyst in the circulating catalyst slurry is 3.8%. The organic phase is a toluene-benzaldehyde oxime solution, which overflows into a storage tank and is sent to the next process.

[0168] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the benzaldehyde conversion rate decreased to below 99.0%, the feeding of benzaldehyde, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. Gas chromatography was used for analysis. Conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0169] Example 5

[0170] The method is the same as in Example 1, except that the amount of hydrogen peroxide (70% by mass) added is 20 g / h, the volume ratio of aqueous phase to organic phase is 4.6:1, the amount of filtrate extracted is controlled by a pump to be 19.7 g / h (accounting for 3.2% of the mass of aqueous phase in the product stream), and the mass fraction of oxime in the filtrate is 0.95%.

[0171] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the cyclohexanone conversion rate decreased to below 99.6%, the feeding of cyclohexanone, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. Gas chromatography was used for analysis. Conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0172] Example 6

[0173] The system shown in Figure 1 is adopted.

[0174] Cyclohexanone, ammonia, and hydrogen peroxide are introduced into a reactor and reacted at a temperature of 89-91℃ and a pressure of 0.4MPa. The effective volume of the reactor is 300mL, and it contains 8g of TS-1 titanium-silicon molecular sieve catalyst. The feed rates are: cyclohexanone 35g / h, ammonia 8g / h, and hydrogen peroxide (35% hydrogen peroxide by mass) 40g / h. The product stream overflows from the reactor outlet, mixes with toluene, and is sent to an extraction separator at a toluene flow rate of 120g / h. A sintered metal filter with a filtration accuracy of 10-20 μm is installed in the extraction separator. The material is stirred and mixed for extraction at 50℃. The volume ratio of aqueous phase to organic phase is 3.7:1. Simultaneously, part of the aqueous phase is separated by the filter, and the filtration rate is controlled by a pump at 40.4 g / h (accounting for 6.3% of the aqueous phase mass in the product material). The oxime mass fraction in the filtrate is 0.85%. The filtrate is sent to the next process as wastewater. The remaining mixture overflows into the catalyst separator, where it is separated into organic and aqueous phases. The catalyst separator is equipped with a stirrer in the aqueous phase section, and the stirring speed is controlled at 130 rpm. The aqueous phase containing the catalyst is circulated back to the reactor. The mass fraction of the catalyst in the circulating catalyst slurry is 2.0%. The organic phase is a toluene-cyclohexanone oxime solution, which overflows into a storage tank and is sent to the next process.

[0175] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the cyclohexanone conversion rate decreased to below 99.6%, the feeding of cyclohexanone, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. Gas chromatography was used for analysis. Conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0176] Example 7

[0177] The method is the same as in Example 1, except that a liquid silicon-containing additive (silica sol solution) is added to make the initial silicon content in the aqueous phase of the reactor 300 ppm, the volume ratio of aqueous phase to organic phase 4.8:1, and the pump is used to control the extraction and filtration rate to 50.6 g / h (accounting for 7.8% of the mass of aqueous phase in the product stream). The mass fraction of oxime in the filtrate is 0.97%, and the filtrate is sent to the next process as wastewater.

[0178] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the cyclohexanone conversion rate decreased to below 99.6%, the feeding of cyclohexanone, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. Gas chromatography was used for analysis. Conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0179] Example 8

[0180] The method is the same as in Example 1, except that cyclohexanone is mixed with the catalyst-containing aqueous phase recycled back to the reactor and then fed into the reaction vessel.

[0181] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the cyclohexanone conversion rate decreased to below 99.6%, the feeding of cyclohexanone, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. The conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0182] Example 9

[0183] The system shown in Figure 1 is adopted.

[0184] Cyclohexanone, ammonia, and hydrogen peroxide are introduced into a reactor and reacted at a temperature of 89-91℃ and a pressure of 0.4MPa. The effective volume of the reactor is 300mL, and it contains 10g of TS-1 titanium-silicon molecular sieve catalyst. The feed rates are: cyclohexanone 35g / h, ammonia 8g / h, and hydrogen peroxide (35% hydrogen peroxide by mass) 40g / h. The product stream overflows from the reactor outlet, mixes with toluene, and is sent to an extraction separator at a toluene flow rate of 160g / h. A sintered metal filter with a filtration accuracy of 10-20 μm is installed in the extraction separator. The material is stirred and mixed for extraction at 50℃. The volume ratio of aqueous phase to organic phase is 1.8:1. Simultaneously, part of the aqueous phase is separated by the filter, and the filtration rate is controlled by a pump at 40.4 g / h (accounting for 10.4% of the aqueous phase mass in the product material). The oxime mass fraction in the filtrate is 0.80%. The filtrate is sent to the next process as wastewater. The remaining mixture overflows into the catalyst separator, where it is separated into organic and aqueous phases. The catalyst separator is equipped with a stirrer in the aqueous phase section, and the stirring speed is controlled at 130 rpm. The aqueous phase containing the catalyst is recycled back to the reactor. The organic phase is a toluene-cyclohexanone oxime solution, which overflows into a storage tank and is sent to the next process.

[0185] Under the above process conditions, sampling and analysis were initiated after 10 hours of operation (the conversion rate and selectivity at this point are recorded as the initial conversion rate and selectivity). Subsequently, sampling and analysis of the organic phase effluent from the catalyst separator were conducted every 10 hours. When the cyclohexanone conversion rate decreased to below 99.6%, the feeding of cyclohexanone, ammonia, and hydrogen peroxide was stopped; the conversion rate and selectivity at this point are recorded as the final conversion rate and selectivity. The unit operating time was recorded, and catalyst consumption was calculated. The conversion rate, selectivity, catalyst consumption, and unit operating time data are shown in Table 1.

[0186] Table 1

[0187] As can be seen from the results in Table 1, the present invention is applicable to the ammonoximation reaction of various carbonyl compounds. Under the premise of obtaining high carbonyl compound conversion rate and high oxime selectivity, it can continuously and efficiently separate reaction products, wastewater and catalyst. The device operates stably for a long time and has low catalyst consumption.

[0188] A comparison between Example 1 and Comparative Example 1 shows that the product stream of Comparative Example 1, which uses a method of first filtering and then extracting the reaction product, has a high oxime content in the filtrate, which is 6.4 times that of Example 1, resulting in oxime loss; the catalyst is prone to sticking to the wall, the filter is prone to clogging, and the filtration operation is difficult to control; moreover, the system volume increases, the effective catalyst concentration in the reactor decreases, the device operating time is significantly shortened, catalyst consumption increases, and energy consumption increases.

[0189] A comparison between Example 1 and Comparative Example 2 shows that the product stream of Comparative Example 2, which uses extraction and separation followed by filtration, increases the system volume, reduces the effective catalyst concentration in the reactor, shortens the device operating time, increases catalyst consumption, and increases energy consumption.

[0190] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for the ammonoximation of a carbonyl compound, characterized in that, The method includes: (1) The reactant stream containing carbonyl compound, ammonia and hydrogen peroxide is contacted with a catalyst to carry out an ammonium oxime reaction to obtain the product stream; (2) The product stream is mixed with an organic solvent, and then extracted and filtered simultaneously under disturbed conditions to obtain wastewater and a mixture stream; (3) The mixture stream is separated to obtain an oxime-containing organic phase and a catalyst-containing aqueous phase, and the catalyst-containing aqueous phase is returned to step (1) to provide at least a portion of the catalyst.

2. The method according to claim 1, wherein, The carbonyl compound is selected from C3-C4. 10 Aliphatic ketones, C5-C 10 Alicyclic ketones, C6-C 10 Aromatic ketones, C5-C 10 Alicyclic aldehydes, C6-C 10 At least one of the aromatic aldehydes, preferably at least one of cyclohexanone, acetone, methyl ethyl ketone, cyclopentanone, acetophenone, p-hydroxyacetophenone, furfural, benzaldehyde and p-methylbenzaldehyde; Preferably, the catalyst comprises a titanium-silicon molecular sieve selected from at least one of TS-1, TS-2, Ti-ZSM-5, Ti-ZSM-12, Ti-ZSM-48, Ti-β, Ti-MCM-41, Ti-MOR, Ti-MWW and Ti-SBA-15.

3. The method according to claim 1 or 2, wherein, The reaction stream in step (1) further includes a liquid silicon-containing additive, which is selected from inorganic silicon-containing substances and / or organic silicon-containing substances; Preferably, the inorganic silicon-containing material is silicon oxide and / or silicate, and the organic silicon-containing material is silicate ester and / or silane; Preferably, the amount of the liquid silicon-containing additive used is such that the silicon concentration in the reaction stream is 0.1-10000 ppm.

4. The method according to any one of claims 1-3, wherein, In step (1), the molar ratio of the carbonyl compound, hydrogen peroxide, and ammonia is 1:(1-2):(1-3), preferably 1:(1-1.5):(1-2); Preferably, the hydrogen peroxide is provided by hydrogen peroxide solution, wherein the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 10-80%, preferably 20-70%; Preferably, in step (3), the mass fraction of the catalyst in the aqueous phase containing the catalyst returned from step (1) is 0.5-15%, preferably 2-10%; Preferably, the temperature of the ammonium oxime reaction in step (1) is 50-100℃, more preferably 60-95℃, and the reaction pressure is 0-1MPa, more preferably 0.1-0.6MPa; Preferably, no additional organic solvent is introduced in the ammonium oxime reaction described in step (1).

5. The method according to any one of claims 1-4, wherein, In step (2), the organic solvent is selected from organic solvents that are insoluble or slightly soluble in water, preferably C6-C. 12 Alkanes, C5-C 11 Cycloalkanes, C6-C 10 At least one of aromatic hydrocarbons and C6-C8 alcohols; Preferably, the mass ratio of the organic solvent to the oxime in the product stream is (1-10):1, more preferably (1-6):

1.

6. The method according to any one of claims 1-5, wherein, In step (2), the extraction temperature is 20-90℃, preferably 40-80℃; Preferably, in step (2), the filtration accuracy is 0.01-50μm, more preferably 2-30μm; Preferably, in step (2), the mass fraction of oxime in the wastewater is 0.01-3%, more preferably 0.01-2%; Preferably, in step (2), the ratio of the volume of the aqueous phase in the product stream to the sum of the volumes of the organic solvent and the organic phase in the product stream is greater than 1:1, and more preferably greater than or equal to 1.05:

1. Preferably, in step (2), the amount of wastewater filtered out is controlled to be 2-25 wt%, preferably 3-20 wt%, based on the mass of the aqueous phase in the product stream.

7. The method according to any one of claims 1-6, wherein, The extraction and filtration in step (2) are carried out in an extraction separator, which is equipped with a filter; Preferably, the filter is made of ceramic or metal, and more preferably metal; Preferably, the separation in step (3) is carried out in a catalyst separator, wherein the aqueous phase section of the catalyst separator is equipped with a stirrer for stirring the aqueous phase containing the catalyst.

8. The method according to any one of claims 1-7, wherein, In step (1), the carbonyl compound is mixed with the aqueous phase containing the catalyst returned from step (1), and then contacted with ammonia, hydrogen peroxide and the catalyst; Preferably, the feed ratio of the carbonyl compound and the catalyst-containing aqueous phase returned to step (1) is 1:5-50 by mass.

9. An ammonoxime system for carbonyl compounds, characterized in that, The system includes a carbonyl compound supply unit, an ammonia supply unit, a hydrogen peroxide supply unit, an organic solvent supply unit, an ammonium oxime reaction unit, an extraction separator, and a catalyst separator; The ammonium oximation reaction unit includes at least one reactor for contacting carbonyl compounds, ammonia, and hydrogen peroxide from the carbonyl compound supply unit, the ammonia supply unit, and the hydrogen peroxide supply unit with a catalyst to carry out an ammonium oximation reaction, thereby obtaining a product stream. The outlet of the ammonium oxime reaction unit is connected to the inlet of the extraction separator through a mixing pipeline. The extraction separator is equipped with a filter, a wastewater outlet, and a mixture flow outlet, which are used to simultaneously extract and filter the material from the mixing pipeline to obtain wastewater and mixture flow. The mixing pipeline is provided with an organic solvent inlet connected to the organic solvent supply unit, which is used to mix the product stream of the ammonium oxime reaction with the organic solvent and then send it into the extraction separator. The feed inlet of the catalyst separator is connected to the mixture outlet of the extraction separator, and is used to send the mixture stream from the extraction separator into the catalyst separator; The catalyst separator is equipped with an organic phase outlet and an aqueous phase outlet, which are used to separate the mixture stream from the extraction separator to obtain an oxime-containing organic phase and a catalyst-containing aqueous phase. The aqueous phase outlet is connected to the ammonium oximation reaction unit through a circulation pipeline, which is used to return the catalyst-containing aqueous phase to the reactor.

10. The system according to claim 9, wherein, The ammonium oxime reaction unit includes 1-4 reactors, preferably 1-2 reactors; Preferably, the reactor is a stirred tank reactor; Preferably, each reactor is independently connected to a hydrogen peroxide supply unit; Preferably, the system further includes an additive supply unit for supplying liquid silicon-containing additives to the ammonium oxime reaction unit.

11. The system according to claim 9 or 10, wherein, In the extraction separator, the filter is made of ceramic or metal, preferably metal; Preferably, the filtration accuracy of the filter is 0.01-50μm, and more preferably 2-30μm.

12. The system according to any one of claims 9-11, wherein, The aqueous phase section of the catalyst separator is equipped with a stirrer for stirring the aqueous phase containing the catalyst. Preferably, the catalyst separator is provided with a gas phase outlet at the top.

13. The system according to any one of claims 9-12, wherein, The catalyst separator includes a vessel body and a stirrer, an inner extension tube, and an inner sleeve disposed within the vessel body. The inner sleeve is fitted inside the inner extension tube and is used to convey the mixture flow to the inner extension tube. The inner extension tube is used to convey the mixture flow to the vessel body for two-phase separation to obtain an organic phase and an aqueous phase. A gas phase balance port is provided on the side wall of the inner extension tube to maintain the gas phase balance of the vessel body. The stirrer is disposed within the aqueous phase portion of the vessel body and is used to stir the aqueous phase.

14. The system according to any one of claims 9-13, wherein, The carbonyl compound supply unit is connected to the circulation pipeline and is used to mix the carbonyl compound with the catalyst-containing aqueous phase from the catalyst separator and then feed it into the reactor.

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