CN1939897A - Separating production of ketoxime by three-phase amino-oximate reaction - Google Patents
Separating production of ketoxime by three-phase amino-oximate reaction Download PDFInfo
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Abstract
Production of ketoxime by three-phase oximation reacting separation is carried out by taking ketone as raw materials, non-homogeneous catalytic oximation reacting for ketone and hydrogen peroxide and amine to obtain ketoxime under existence of insoluble or micro-soluble solvent, separating phase for oximation reactant, separating out heavy-phase reactant from water and circulation utilizing.
Description
Technical field
The present invention relates to a kind of preparation method for separating and preparing of ketoxime, illustrating further is to be raw material with ketone, separates the preparation ketoxime by the preparation of liquid-liquid-solid three-phase amidoxime.
Background technology
Aliphatic ketone or aromatic ketone all can with the derivative such as the azanol generation condensation reaction of ammonia, generate corresponding ketoxime, use Beckmann again and reset and can synthesize a series of acid amides.Wherein, rearrangement of cyclohexanone-oxime system hexanolactam has important industrial significance.
Hexanolactam, the formal name used at school ε-Ji Neixianan is a kind of important petrochemicals, is widely used in making polyamide fibre and engineering plastics.The hexanolactam industrial process mainly contains pimelinketone-hydroxylamine assay, photo-nitrosation of cyclohexane process and toluene method etc.Wherein pimelinketone-hydroxylamine assay is the present industrial method that generally is used for producing cyclohexanone-oxime, and it has accounted for more than 90% of hexanolactam world device overall throughput.Because the technology difference of preparation azanol, pimelinketone-azanol operational path mainly contain three kinds of oxammonium sulfate method (HSO method), nitric oxide reduction method (NO method) and phosphatic hydroxylamine methods (HPO method) again.
There is the shortcoming of two aspects in above-mentioned method by hydroxylammonium salt multistep synthesizing cyclohexane 1 ketoxime: (1) reaction process complexity, and technical process is long; (2) technology by-product inorganic ammonium salt discharges a large amount of oxynitride and oxysulfide, etching apparatus and contaminate environment.Since the end of the seventies, many companies have carried out number of research projects for improving the cyclohexanone-oxime production technique, it wherein is the amidoxime metallization processes flow process weak point of raw material with pimelinketone, ammonia and oxygen (perhaps hydrogen peroxide), complicated azanol building-up process and the generation of SOx or NOx have been avoided, and by-product sulphur ammonium not, environmentally friendly, have application value most.As the gas phase ammonoxidation method that Allied chemical company proposes, the cationic exchange membrane process that Mitsubishi proposes etc.
1988, U.S. Pat 4745221 discloses pimelinketone and ammonia in the liquid phase generate cyclohexanone-oxime by hydrogen peroxide oxidation method for the first time: with TS-1 is catalyzer, hydrogen peroxide is an oxygen source, under 60 ℃～80 ℃ mild conditions, pimelinketone selectivity 98.2%, hydrogen peroxide selectivity 93.2%.By product is few.U.S. Pat 4894478 discloses the method that adopts the multistep liquid-phase catalysis subsequently, pimelinketone oximate process was divided into for two steps, thereby has improved the yield of cyclohexanone-oxime.
At the mid-90 Arco Chemical Technology, L.P. has proposed the production technique of hydrogen peroxide and the combination of TS-1 catalysis of pimelinketone oxamidine technology, reduces the production cost of hydrogen peroxide.US5451701 and US 5599987 disclose the integrated technique of isopropanol oxidation and cyclohexanone oxamidinating, comprise: isopropanol oxidation, acetone separation, cyclohexanone oxamidinating, solvent recuperation, processes such as acetone hydrogenation, the gained pimelinketone needs extracting and refining, and solvent and excess of ammonia recycle through fractionation by distillation.This integrated patented technology will more sophisticated Virahol hydrogen peroxide method and titanium molecular sieve catalysis cyclohexanone oxamidinating method organically combine, make titanium molecular sieve catalysis cyclohexanone oxamidinating technology stride forward major step again.
Because existing Ammoximation reaction process need add the low-carbon alcohol (for example trimethyl carbinol) of dissolving each other with water as solvent, but selected solvent can not stable existence in the oleum system, must before rearrangement reaction, separate process through repeatedly distilling with extraction etc., ubiquity flow process complexity, energy consumption is big, the oxime stability of solution is poor, deficiencies such as the easy obstruction of fusion oxime pipeline.Chinese patent 200510032184 discloses an improved amidoxime technology, two technologies that inhomogeneous reaction is integrated have been adopted, Beckmann rearrangement reaction solvent for use and oximation reaction solvent phase are together, solvent is containing the rearrangement system energy stable existence of oleum, any reaction can not take place in self, so the oximate product need not to make pure oxime by conventional separation means such as distillation, extractions.
For solving problems such as amidoxime process catalyst separating and efficient, CN02100227 and CN02100228 disclose amidoxime product and the isolating method of catalyzer continuous sedimentation, and catalyst recirculation is used, and has improved the hydrogen peroxide utilization ratio, realize the industrialization of novel process.On the other hand, because catalyzer dissolves loss in the basic solution of Ammoximation reaction, the time of continous-stable operation and separating of catalyzer will be had influence on.EP0496385 has reported the method for intermittently taking out decaying catalyst and fresh makeup catalyst, CN03137914 discloses a kind of inhibition catalyst loss, prolong the method for catalyst life, add liquid state at the oxamidinating reaction system that contains Si catalyst and contain silicon additive, make the silicon in the solution reach equilibrium concentration, the silicon of catalyzer runs off and obviously reduces.
But, for the amidoxime metallization processes of continuous operation, suppress become estranged catalyzer and the isolating method of reaction solution of catalyst stream at present and have following problem:
(1) add contain silicon additive after, the silicon of catalyzer runs off still inevitable, dissolved silicon with reaction product and catalyst separating after by trimethyl carbinol distillation and toluene extraction, mostly discharge, so auxiliary agent need be constantly additional with water.
(2) the catalyst raw powder particle diameter mostly is 0.1-0.3 μ m in the reaction solution, adopt spinning liquid to be difficult to thorough the separation with subsidence style, cause catalyst loss, and when adopting means such as membrane sepn, because the too small segregational load that causes of particle is overweight, and catalyzer is easy swelling under alkaline condition, causes fenestra to stop up the operate continuously difficulty.
Summary of the invention
The objective of the invention is to utilize the characteristics of heterogeneous amidoxime rearrangement technology, a kind of the deficiencies in the prior art that overcome are provided, the three-phase Ammoximation reaction that solves reaction system catalyst loss inactivation and catalyst separating difficulty separates the method for preparing ketoxime synchronously, prolong catalyst life and operational cycle, serialization production preferably.
The objective of the invention is to realize by following manner:
Under the condition of solid catalyst and the existence of insoluble with water or sl. sol. solvent, ketone, hydrogen peroxide and ammonia are carried out the reaction of liquid-liquid-solid three-phase using nonhomogeneous phase oximation generate ketoxime; After the phase-splitting of oximation reaction product, light mutually for containing the solvent phase of ketoxime, recycle behind the direct cutting out partial water of heavy phase; Or, recycle after will containing the heavy phase extracting phase cutting out partial water of catalyzer heavy phase insoluble with water or sl. sol. solvent extraction ketoxime wherein.
In method provided by the invention, described ketone is aliphatic ketone, or cyclic aliphatic ketone, or aromatic ketone; Described and the immiscible or sl. sol. solvent of water is alkane or naphthenic hydrocarbon or aromatic hydrocarbons, or their mixture.Carbonatoms 3～10 aliphatic ketones preferably, or the cyclic aliphatic ketone of carbonatoms 6～10 or aromatic ketone; Preferred and the immiscible or sl. sol. reaction solvent of water is a carbonatoms 4～10 alkane or naphthenic hydrocarbon or aromatic hydrocarbons, or their mixture.
In method provided by the invention, the ketoxime preparation separates by oximation reaction, product and three steps of water sepn realize;
The oximation reaction step is to be raw material with pimelinketone, hydrogen peroxide and ammonia, under the condition that HTS and insoluble with water or sl. sol. solvent exist, generates cyclohexanone-oxime by the liquid-liquid-solid three phase catalytic reaction; At the product separating step, reaction product is divided into the weight two-phase by decantation, and light mutually for containing the solvent phase of cyclohexanone-oxime, heavy phase directly enters the water sepn step, or after using insoluble with water or sl. sol. solvent extraction cyclohexanone-oxime wherein, its heavy phase extracting phase enters the water sepn step again; The water sepn step be for containing the heavy phase of catalyzer and water or heavy phase extracting phase by concentrating or concentratedly separating with liquid-solid, remove part moisture after, recycle.
Extraction phase gently enters follow-up related process mutually with oximation reaction.
1 be illustrated with reference to the accompanying drawings:
(I) under the condition that HTS exists, with pimelinketone (1), hydrogen peroxide (2) and ammonia (3) is raw material, and with alkane or naphthenic hydrocarbon or aromatic hydrocarbons, or their mixture is reaction solvent (4), in the R of oximation reaction system, generate cyclohexanone-oxime by three-phase catalysis, described reaction solvent is taken from the alkane or the naphthenic hydrocarbon of carbonatoms 4～10, or the aromatic hydrocarbons of carbonatoms 6～9, or their mixture, preferred hexanaphthene, or normal hexane, or toluene, or 2～3 mixture wherein.By percentage to the quality, solvent accounts for the amount 20%～80% of reactant, and 60～80 ℃ of oximation reaction temperature, the mol ratio of hydrogen peroxide and pimelinketone are 1.0～1.2.
(II) oximation reaction product (5) enters product separation system S1a, and light phase (6) is cyclohexanone-oxime and solvent; Heavy phase (7) is a small amount of cyclohexanone-oxime, water and catalyzer, enter separation system S1b, with the solvent identical (8) extraction heavy phase with reaction solvent, described heavy phase product extracting operation temperature is 10～100 ℃, working pressure is 0.1～0.5Mpa (abs), preferred 30～80 ℃, 0.1～0.2Mpa (abs).Extracting phase (9) enters water separating system for containing the water of catalyzer, enters subsequent technique after extraction phase (10) and light (6) mutually mixing.
(III) the separating obtained material of product concentrates by evaporation or component distillation in water separating system S2a, removes part moisture (12), and aqueous catalyst solution (13) is circulated to the R of oximation reaction system.Perhaps, material after concentrating is divided into two strands, solution (13) is circulated to the R of oximation reaction system, solution (11) carries out spinning liquid through S2b to be separated, or centrifugation, or liquid-solid lock out operation such as membrane sepn, high concentration catalyst (15) is circulated to the R of oximation reaction system, liquid phase (14), is discharged with waste water formation behind the recovery solvent wherein through stripping.
The moisture quality that described water sepn partly removes and the ketone mass ratio of oximation reaction are 0.5: 1～5: 1, preferred 1: 1～3: 1.
The liquid-solid separation of described water sepn part can be intermittence or continuous mode, and the moisture quality of liquid-solid separation removal is 0.001～2: 1 with concentrating the moisture mass ratio that removes, preferred 0.01～0.1: 1.
The working pressure of described thickening is 0.001～0.2Mpa (abs), and service temperature is 10～110 ℃, preferred 0.005～0.08Mpa (abs), 40～80 ℃.
The solvent of described component distillation is got the ketone of oximation reaction, or reaction solvent, or their mixture, preferred pimelinketone, or hexanaphthene, or normal hexane, or benzene, or toluene, or 1～2 mixture wherein.
The explanation of accompanying drawing 2, identical with accompanying drawing 1 with the water sepn step at oximation reaction, difference is:
(II) oximation reaction product (5) enters product separation system S1 decantation, and light phase (6) is cyclohexanone-oxime and solvent, enters subsequent technique; Heavy phase (7) is a small amount of cyclohexanone-oxime, water and catalyzer, enters water separating system.
The Chinese patent 200510032184 of previous application discloses the integrated technique of preparing amide using nonhomogeneous phase oximation rearrangement.Be and the present invention is directed to important innovation of amidoximeization: the ingenious characteristics of having utilized the using nonhomogeneous phase oximation reaction product mainly to be distributed in light phase (with the immiscible or sl. sol. solvent phase of water) of contriver, mutually light in the present invention or mutually light and heavy phase extraction phase is sent into subsequent technique in the lump, recycle after dewatering by concentrating and contain the heavy phase of catalyzer or heavy phase extracting phase, silicon can not cause loss with the water system of discharging, and has solved the difficult problem of catalyst deactivation and catalyst separating synchronously.
Contrast is the cyclohexanone oxamidinating technology of solvent with the trimethyl carbinol, and method provided by the present invention mainly embodies following difference:
(1) employing and the immiscible or sl. sol. solvent of water are as the Ammoximation reaction solvent, and the product ketoxime mainly is distributed in solvent phase, and the low amounts of product that is distributed in water is by the extraction recovery or by circulating behind the separation moisture;
(2) the catalyst separating step of slurry attitude reaction product in the former technology of cancellation, the solution circulated that contains catalyzer is used, by the water yield of thickening with the balance recycle stock;
(3) reserve the liquid-solid separation of little treatment capacity, intermittently or in minimum ratio drainage water, with water-soluble heavy seeds in the equilibrium system.
The technology that liquid-liquid-solid three-phase Ammoximation reaction provided by the invention separates the preparation ketoxime has bigger improvement and simplification with respect to original technology, can simplify the operation widely, saves cost, produces good economic worth, particular embodiment in the following areas:
(1) having omitted is the extensive continuous film separation of the necessary catalyzer of amidoxime metallization processes or the filtering separation of solvent with the low-carbon alcohol, for the catalyst grain size slurry attitude material of 0.1～0.3 μ m only, the material of isolating behind the ketoxime concentrates circulation, has overcome the susceptible to plugging shortcoming of existing technology, and is easy to operate.
(2) concentrate dewater after do not run off because silicon does not efflux with water, catalyst deactivation speed significantly descends, but prolong operation cycle correspondingly also can reduce greatly even cancel and contains the additional of silicon additive.
(3) silicon of trace impurity and loss can not enter subsequent technique with ketoxime, and product quality is more secure.
Description of drawings
Accompanying drawing 1 is for the invention provides amidoxime metallization processes schema.In accompanying drawing 1, R is an oximation reaction, and S1a is that product separates with S1b, and S2a and S2b are water sepn.
Accompanying drawing 2 is for the invention provides alternative amidoxime metallization processes schema.In accompanying drawing 2, R is an oximation reaction, and S1 is that product separates, and S2a and S2b are water sepn.
Embodiment
Just the present invention will be further described for the following examples, and should not be interpreted as limitation of the scope of the invention.
Embodiment 1: add titanium-silicon molecular sieve catalyst 2.5g, pimelinketone 15.0g and hexanaphthene 25.0g in advance in the glass reaction still of 250ml band magnetic agitation.After being warming up to 69 ℃, it is that 27.5% hydrogen peroxide 20.8g and concentration are 25% ammoniacal liquor 22.9g that beginning at the uniform velocity drips concentration, and reaction is 2 hours under alkane water azeotropic temperature, and the reinforced back that finishes prolongs reaction 1 hour.Remain on and use fresh cyclohexane extraction product 3 times more than 60 ℃, the hexanaphthene consumption is 25.0g/ time, and it is standby to isolate extracting phase 40.8g, and extraction phase gently mixes mutually with reaction product, gets cyclohexanone-oxime-cyclohexane solution.By the pimelinketone in this solution of gas chromatographic analysis and the content of cyclohexanone-oxime, calculate reaction result and see Table 1.
Embodiment 2: repeat embodiment 1, what difference was to add in advance is not the fresh titanium silicalite molecular sieve catalyst, but the extracting phase among the embodiment 1.Isolate extracting phase 79.1g after the reaction product extraction, by the Rotary Evaporators transpiring moisture, pressure is 0.01Mpa, and temperature is 50 ℃, and concentrating back weight is 40.1g.By the gas chromatographic analysis product, reaction result sees Table 1.
Table 1
| The experiment number | The catalyst recirculation number of times | Catalyzer accumulated running time h | Pimelinketone transformation efficiency % | Cyclohexanone-oxime selectivity % | Hydrogen peroxide utilization |
| Embodiment | |||||
| 1 | 0 1 10 20 30 40 | 3 6 33 63 93 123 | 98.4 98.2 98.4 98.4 98.3 98.2 | 99.5 99.4 99.5 99.2 99.3 99.4 | 89.3 90.1 90.2 90.1 90.2 90.2 |
Embodiment 7: hydrogen peroxide, pimelinketone-cyclohexane solution, the recirculated water that contains HTS join in the reactor that mechanical stirring and condensation reflux unit are housed continuously by the double plunger micro pump respectively, and ammonia is through the adding continuously of mass flowmeter metering back.Hydrogen peroxide concentration is 27.5%, and flow is 68.0g/h, and pimelinketone solution quality concentration is 37.5%, flow is 130.8g/h, and circulating water flow is 285.6g/h, and ammonia flow is 18.7g/h, the useful volume of reactor is 1000ml, about 115min of material residence time in reactor.Temperature of reaction is 69 ℃, and pressure is kept normal pressure.Product overflows reactor, enter extractor after isolating gently mutually by decantation, the add-on of fresh cyclohexane is 245.3g/h, the gained extracting phase is at 0.025MPa, 65 ℃ concentrate down, vapor condensation water is discharged system with the flow velocity of 49.3g/h, and the solution after concentrating is sent reactor cycles back to by peristaltic pump and used.By the product of gas chromatographic analysis difference under working times, the results are shown in Table 2.
Comparative Examples 1: repeat embodiment 7, difference is: (1) extracting phase is without evaporation concentration, but directly discharges system; (2) useful volume of reactor is 500ml, to guarantee that under no recirculated water state material residence time in reactor equates substantially with embodiment 7.By the product of gas chromatographic analysis difference under working times, the results are shown in Table 2.
| Continuous operating | Embodiment | 7 | Comparative Examples 1 | |||
| Pimelinketone transformation efficiency % | Cyclohexanone-oxime selectivity % | Pimelinketone transformation efficiency % | Cyclohexanone-oxime selectivity % | |||
| 20 40 60 80 100 | 98.3 98.2 98.3 98.3 98.2 | 99.4 99.5 99.3 99.4 99.4 | 97.9 97.8 97.6 91.7 91.0 | 99.8 98.7 99.0 98.0 97.8 | ||
Embodiment 8: add benzene 20.0g in advance in the glass reaction still of 250ml band magnetic agitation, methylethylketone 10.1g, HTS 1.2g is warming up to 65 ℃ after the mixing fully, at the uniform velocity drips the ammoniacal liquor 21.0g of the hydrogen peroxide 19.8g and 25% (weight ratio) of 27.5% (weight ratio) in 2 hours.Be controlled at 68.9 ℃ of reactions down of ternary azeotropic temperature, the reinforced back that finishes prolongs reaction 1 hour.After standing separation goes out gently mutually,, obtain extracting phase 38.0g with fresh benzene extraction heavy phase 3 times.10g benzene is joined in the extracting phase, 60 ℃ of following benzene water component distillations, the vapor condensation phase-splitting gets benzene 3.5g, and water 36.5g, still liquid are the benzene that contains catalyzer, and oximation reaction is carried out in circulation.Circulate after 10 times, gas chromatographic analysis oximation reaction product, methylethylketone transformation efficiency are 99.1%, and the methyl ethyl ketoxime selectivity is 97.9%.
Embodiment 9: add hexanaphthene 40.0g in advance in the glass reaction still of 500ml band magnetic agitation, methylethylketone 21.1g, HTS 2.5g is warming up to 60 ℃ after the mixing fully, at the uniform velocity drips the ammoniacal liquor 44.8g of the hydrogen peroxide 40.2g and 25% (weight ratio) of 28.5% (weight ratio) in 2.5 hours.Be controlled at 63.6 ℃ of reactions down of ternary azeotropic temperature, the reinforced back that finishes prolongs reaction 1 hour.Standing separation obtains heavy phase 77.9g after going out gently mutually.Heavy phase is at 0.010MPa, 50 ℃ of following rotary evaporations, and vapor condensation divides water 70.5g, and remnants are catalyzer, a spot of ketoxime and water, and oximation reaction is carried out in circulation.Circulate after 5 times, gas chromatographic analysis oximation reaction product, methylethylketone transformation efficiency are 98.4%, and the methyl ethyl ketoxime selectivity is 97.1%.
Claims (11)
1, a kind of three-phase Ammoximation reaction separates the method for preparing ketoxime, under the condition of solid catalyst and the existence of insoluble with water or sl. sol. solvent, ketone, hydrogen peroxide and ammonia is carried out the reaction of liquid-liquid-solid three-phase using nonhomogeneous phase oximation generate ketoxime; After the phase-splitting of oximation reaction product, light mutually for containing the solvent phase of ketoxime, recycle behind the direct cutting out partial water of heavy phase; Or, recycle after will containing the heavy phase extracting phase cutting out partial water of catalyzer heavy phase insoluble with water or sl. sol. solvent extraction ketoxime wherein.
2, a kind of three-phase Ammoximation reaction according to claim 1 separates the method for preparing ketoxime, and described ketone is aliphatic ketone or cyclic aliphatic ketone or aromatic ketone; Described insoluble with water or sl. sol. solvent is alkane or naphthenic hydrocarbon or aromatic hydrocarbons, or their mixture.
3, the method for a kind of three-phase Ammoximation reaction separation of ketoxime according to claim 2, described ketone are carbonatoms 3～10 aliphatic ketones, or the cyclic aliphatic ketone of carbonatoms 6～10 or aromatic ketone; Alkane or naphthenic hydrocarbon or aromatic hydrocarbons that described insoluble with water or sl. sol. solvent is a carbonatoms 4～10, or their mixture.
4, a kind of three-phase Ammoximation reaction according to claim 1 separates the method for preparing ketoxime, and technology is by oximation reaction, and product separates and three steps of water sepn are formed; The oximation reaction step is to be raw material with pimelinketone, hydrogen peroxide and ammonia, under the condition that HTS and insoluble with water or sl. sol. solvent exist, generates cyclohexanone-oxime by the liquid-liquid-solid three phase catalytic reaction; At the product separating step, reaction product is divided into the weight two-phase by decantation, and light mutually for containing the solvent phase of cyclohexanone-oxime, heavy phase directly enters the water sepn step, or after using insoluble with water or sl. sol. solvent extraction cyclohexanone oxime wherein, its heavy phase extracting phase enters the water sepn step again; The water sepn step be for containing the heavy phase of catalyzer and water or heavy phase extracting phase by concentrating or concentratedly separating with liquid-solid, remove part moisture after, recycle.
5, a kind of three-phase Ammoximation reaction according to claim 4 separates the method for preparing ketoxime, and described insoluble with water or sl. sol. solvent is alkane or naphthenic hydrocarbon or aromatic hydrocarbons, or their mixture.
6, a kind of three-phase Ammoximation reaction according to claim 5 separates the method for preparing ketoxime, and described reaction solvent is taken from the alkane or the naphthenic hydrocarbon of carbonatoms 4～10, or the aromatic hydrocarbons of carbonatoms 6～9, or their mixture.
7, a kind of three-phase Ammoximation reaction according to claim 4 separates the method for preparing ketoxime, and in the water sepn step, the mass ratio of total moisture that removes and oximation reaction ketone is 0.5: 1～5: 1.
8, a kind of three-phase Ammoximation reaction according to claim 4 separates the method for preparing ketoxime, and the mass ratio of the moisture of the liquid-solid separation removal in the water sepn step and oximation reaction ketone is 0.001～2: 1.
9, a kind of three-phase Ammoximation reaction according to claim 4 separates the method for preparing ketoxime, and described extracting phase concentration method is evaporation or component distillation; The solid separation method of extracting phase is that spinning liquid separates, or centrifugation, or membrane sepn.
10, a kind of three-phase Ammoximation reaction according to claim 9 separates the method for preparing ketoxime, and the solvent of extracting phase component distillation is got the ketone of oximation reaction, or insoluble with water or sl. sol. solvent solvent, or their mixture.
11, a kind of three-phase Ammoximation reaction according to claim 4 separates the method for preparing ketoxime, and the liquid-solid isolated water of extracting phase is discharged behind the recovery solvent wherein by stripping, no longer loops back oximation reaction.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838510A (en) * | 2012-09-07 | 2012-12-26 | 福建锦江石化有限公司 | Method and device for filtering and separating reaction system catalyst for preparing cyclohexanone-oxime |
| WO2018157617A1 (en) * | 2017-03-03 | 2018-09-07 | 山东省化工研究院 | Process method for synthesis of ketoxime |
| CN110156701A (en) * | 2019-06-25 | 2019-08-23 | 吴赣药业（苏州）有限公司 | A kind of synthetic method of 2,3,5,6- Tetramethylpyrazine |
| CN110498748A (en) * | 2019-09-17 | 2019-11-26 | 万华化学集团股份有限公司 | L-arginine and its derivative are used to prepare the purposes and a kind of method for preparing cyclododecanone oxime of cyclododecanone oxime |
| WO2022073525A1 (en) | 2020-11-02 | 2022-04-14 | 湖北金湘宁化工科技有限公司 | Method for integrating ammoximation reaction and separation and device thereof |
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2006
- 2006-09-27 CN CNB200610032322XA patent/CN100506787C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838510A (en) * | 2012-09-07 | 2012-12-26 | 福建锦江石化有限公司 | Method and device for filtering and separating reaction system catalyst for preparing cyclohexanone-oxime |
| CN102838510B (en) * | 2012-09-07 | 2015-05-27 | 福建锦江石化有限公司 | Method and device for filtering and separating reaction system catalyst for preparing cyclohexanone-oxime |
| WO2018157617A1 (en) * | 2017-03-03 | 2018-09-07 | 山东省化工研究院 | Process method for synthesis of ketoxime |
| US10654795B2 (en) | 2017-03-03 | 2020-05-19 | Chemical Technology Academy Of Shandong Province | Method for synthesizing ketoxime |
| CN110156701A (en) * | 2019-06-25 | 2019-08-23 | 吴赣药业（苏州）有限公司 | A kind of synthetic method of 2,3,5,6- Tetramethylpyrazine |
| CN110498748A (en) * | 2019-09-17 | 2019-11-26 | 万华化学集团股份有限公司 | L-arginine and its derivative are used to prepare the purposes and a kind of method for preparing cyclododecanone oxime of cyclododecanone oxime |
| WO2022073525A1 (en) | 2020-11-02 | 2022-04-14 | 湖北金湘宁化工科技有限公司 | Method for integrating ammoximation reaction and separation and device thereof |
| CN114436889A (en) * | 2020-11-02 | 2022-05-06 | 湖北金湘宁化工科技有限公司 | Ammoximation reaction and separation integrated method and device thereof |
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