CN103801400B - A kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling - Google Patents
A kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling Download PDFInfo
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Abstract
A kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling, configure phosphorus trichloride solution in organic solvent, and add phenol raw material, magnetic metal powder is added in the mixed solution containing phosphorus trichloride, phenol and organic solvent simultaneously; Reaction adopts reactive distillation to be coupled with magnetic stablizing bed, phosphorus trichloride and phenol generate single phosphite ester presoma by reactive distillation fast eliminating hydrogen chloride, simultaneously outside is forced magnetic field and is coupled with reactive distillation, form magnetic stable state, fully contact when magnetic metal powder is reacted with phosphite ester presoma, reactive distillation synthesizes single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling.
Description
Technical field
The invention belongs to chemical production technology technical field, relate to a kind of reactive distillation particularly and synthesize the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling.
Background technology
Metal complex catalysts is the solvay-type synthetic catalyst system that transition metal halide and organo-metallic compound form, and belongs to ligand complex structure.Refer to catalyst reactant molecule being activated by coordination.At least containing a metal ion or atom in this kind of catalyst, no matter whether parent itself is complex compound, but time in action, catalytic active center occurs with coordination structure, by changing metal-complexing number or dentate, the rarest a kind of reaction molecular enters co-ordination state and is activated, thus promotes the carrying out of reaction.Homogeneous complex catalysis agent can the complex compound catalyst of melt into homogeneous phase in reaction system.Majority is the salt of metallo-organic compound, transition metal, can the complex compound catalyst of melt into homogeneous phase in reaction system.Preparation is comparatively easy, industrially applies earlier.As Ziegler catalyst (titanium tetrachloride-alkyl aluminum), the Ziegler-Natta catalyst (titanium trichloride-alkyl aluminum) of alkene in the rhodium catalyst, olefinic polyreaction of the palladium catalyst of the cobalt carbonyl catalyst of carbonylation synthesis aldehyde, the cobalt carbonyl catalyst of phosphine-modified and rhodium carbonyl catalyst, ethylene acetaldehyde, Production of Acetic Acid by Methanol Carbonylation, the Raney nickel etc. in conjugated alkene cyclization.
Phosphite ester metallic catalyst belongs to the one of metal combination complex catalyst, is obtained by reacting by phosphite ester and metal precursor.Its presoma phosphite ester compound is a kind of important organic chemical industry's intermediate, can be widely used in and produce brightening agent, lubricant, antioxidant, organophosphorus pesticide and the synthesis for hydrocyanation reaction catalyst system and catalyzing organophosphor metal complex.Because phosphite ester metal combination complex catalyst (phosphorous acid cobalt, phosphorous acid nickel) can have important effect to hydroformylation reaction and cyanogenation, therefore phosphorous acid metallic catalyst causes extensive attention.In formylation reaction, wherein bis-phosphite metallic catalyst can have larger sterically hindered compared with triphenyl phosphorus, adopts phosphite ester can effectively improve the selective of formylation reaction.In adiponitrile reaction, by the hydrocyanation process of butadiene in patent CN101479237A, CN101484417A, butadiene can be converted into allyl acetonitrile and adiponitrile by a kind of bidentate phosphite ligands and multidentate phosphite catalyst.But the technological process of the preparation technology of catalyst and the preparation of monodentate catalyst is not described later in detail.
But there is not report to report the synthesis technique of single phosphite ester at present, simultaneously, consider that the coordinating metal such as iron, cobalt, nickel have stronger magnetic characteristic in single phosphite ester production process, combine the magnetic stablizing bed mode be combined with magnetic metal powder and carry out monodentate phosphite complex catalyst and have not been reported.In traditional handicraft synthesis, the reactor of containing metal powder adopts traditional mechanical agitation, and unreacted solid metal powder utilizes metallic filter, ceramic filter, cyclone hydraulic separators to carry out solid-liquor separation.
Summary of the invention
The present invention is for better to solve the problems of the technologies described above, consider iron in single phosphite catalysts production process, cobalt, the coordinating metal raw materials such as nickel have stronger magnetic characteristic, a kind of reactive distillation is provided to synthesize the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling, magnetic stablizing bedly be different from traditional mechanical agitation and filter centrifugation separating technology fluid bed, also carry out with magnetic-particle being solid phase while adopting reactive distillation to make reactive distillation with the magnetic stablizing bed technique be coupled, the magnetic current of magnetic-particle under additional magnetic fields, solid particle in bed is not do unordered freely-movable in operation, but in ordered arrangement state.Magnetic stablizing bed can stable operation in wider scope, magnetic metal powder is disperseed in the reactor uniformly, can interphase mass transfer be improved.The concrete technical scheme adopted is as follows:
A kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling, configure phosphorus trichloride solution in organic solvent, and add phenol raw material, magnetic metal powder is added in the mixed solution containing phosphorus trichloride, phenol and organic solvent simultaneously; Reaction adopts reactive distillation to be coupled with magnetic stablizing bed, phosphorus trichloride and phenol generate single phosphite ester presoma by reactive distillation fast eliminating hydrogen chloride, simultaneously outside is forced magnetic field and is coupled with reactive distillation, form magnetic stable state, fully contact when magnetic metal powder is reacted with phosphite ester presoma, reactive distillation synthesizes single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling.
For prepare phenol, phosphorus trichloride, organic solution water content not higher than 100ppm.
Organic solvent is cycloalkane and aromatic hydrocarbon, and the addition of organic solution makes the solubility of phosphorus trichloride in organic solution not higher than 40% weight ratio.
The mol ratio of described phenol and phosphorus trichloride is greater than 3:1, and wherein the mol ratio of phenol and phosphorus trichloride exceeds stoichiometry 10% mol ratio.
Described high-intensity magnetic field is uniform magnetic field, and magnetic field intensity is at 3-760KA/m.
Described magnetic metal powder comprises one or more mixing in iron powder, cobalt powder, nickel powder.Particle diameter is 1 micron to 1000 microns, and metal-powder total oxygen is not higher than 100ppm.
Reactive distillation is 50-350 DEG C with the magnetic stablizing bed reaction temperature be coupled, and reaction pressure is-0.1MPaG-0.1MPaG.
Described reactive distillation makes the main reactor volume space velocity of synthetic reaction be not less than 0.1 with the magnetic stablizing bed technique of synthesizing single phosphite ester Metal complex catalysts that is coupled.
A kind of reactive distillation of the present invention is with the preparation technology of the magnetic stablizing bed single phosphorous acid esters Metal complex catalysts be coupled, and described phenol can be metacresol, orthoresol, paracresol, phenol, naphthols, anthrol.
The organic solvent added is cycloalkane and aromatic hydrocarbon and combination, cyclohexane, benzene and toluene can be selected, phosphorus trichloride, excessive phenol are dispersed in organic solvent, on the one hand owing to there being higher dispersiveness, ensure that the addition of organic solution makes the solubility of phosphorus trichloride in organic solution not higher than 40% weight ratio, because phosphorus trichloride reactant concentration reduces, the side reaction between phosphorus trichloride and phenol reduces, and ensures that phosphorus trichloride has higher conversion ratio simultaneously; On the other hand, because the reacting phase of phosphorus trichloride and phenol is when violent, lowers reactant concentration and make to respond that to be in state controlled for danger, suppress reaction acutely to be avoided out of control.Described phenol, phosphorus trichloride, organic solvent raw material need adopt refining way, the methods such as process for purification comprises employing rectifying, absorption, for prepare phenol, phosphorus trichloride, organic solvent water content need control not higher than 100ppm.
Simultaneously, magnetic metal powder is added in the mixed solution containing phosphorus trichloride, phenol and organic solvent, in reactive distillation column, force magnetic field by outside to be coupled with reactive distillation, combine reactive distillation and magnetic stablizing bed advantage, on the one hand, magnetic metal powder forms magnetic stable state, to ensure that magnetic metal powder fully contacts with phosphorous acid presoma, regulate uniform magnetic field intensity at 3-760KA/m, ensure that nickel powder forms the stable orderly suspended state of magnetic; On the other hand, the raw material such as phosphorus trichloride and phenol is generated the hydrogen chloride generated in phosphite ester process and is removed fast by reactive distillation, can improve the speed of single phosphite ester Metal complex catalysts synthesis.Reactive distillation and magnetic stablizing bed coupling technique also accelerate reaction rate, the main reactor volume space velocity that single phosphite ester Metal complex catalysts is reacted is not less than 0.1, and volume space velocity is defined as unit volume reactor and can processes and make phosphorus trichloride transform the volume generating single phosphite ester completely.The volume space velocity of similar reaction is then generally 0.01 even lower.Rectifying column adopts plate column, sieve tray, and avoid solid metal powder to block rectifying column, reaction tower tower reactor reactor adopts magnetic stablizing bed strengthening.Tower reactor discharging increases magnetic separator, metal powder particle in interception discharging, avoid the techniques such as the recoil of traditional handicraft middle filtrator and cyclone hydraulic separators, cleaning, and in traditional liquid, unreacted solid metal powder utilizes metallic filter, ceramic filter, cyclone hydraulic separators to carry out solid-liquor separation.
The particle diameter of above-mentioned magnetic metal powder is 1 micron to 1000 microns, and particle diameter is unfavorable for more greatly the carrying out reacted.Meanwhile, for ensureing that powder total oxygen is not higher than 100ppm, magnetic metal powder needs to consider vacuum outgas, and the techniques such as surface treatment strictly control oxygen content.On the one hand, hydrogen reducing and vacuum outgas are the key factors reducing metal powder oxygen content, and reduction temperature is not less than 400 DEG C usually, add in magnetically stabilized bed reactor and react after metal powder is degassed fast.The pretreated way of magnetic metal powder also comprises alkali cleaning, the alkali cleaning of indication needs the grease on magnetic metal powder surface to remove, alkali lye comprises the highly basic such as NaOH, potassium hydroxide, or the weak base such as calcium hydroxide, ungrease treatment is carried out on powder granule surface, the reaction efficiency that effective raising is magnetic stablizing bed.
Reactive distillation is 50-350 DEG C with the magnetic stablizing bed reaction temperature be coupled, and suitable temperature range is also conducive to the carrying out reacted, and usually selects 160-220 DEG C.Reaction pressure is-0.1MPaG-0.1MPaG.Reactive distillation is in negative pressure, is conducive to reacting the hydrogen chloride generated and removes from reaction system fast.
Meanwhile, adopt reactive distillation and magnetic stablizing bed coupling technique effectively can improve reaction rate, reduce the generation of side reaction.The yield of phosphite ester presoma is not less than 97%, and the yield of phosphite ester Metal complex catalysts is not less than 95%.
Coupled reactor external magnetic field control described in description of the present invention is the magnetic stablizing bed form of expression.
The invention has the beneficial effects as follows: compared with traditional mechanical agitation, magnetic stablizing bed more difficult blocking is attached on wall and interior panelling, and magnetic presents ordered arrangement, magnetic powder gap uniformity, is not easy to produce channel, and reaction efficiency improves.And magnetic metal powder is easily passed through Magneto separate characteristic by follow-up lock out operation preferably, simplifies operating process, reduces running cost.And the reactants such as phosphorus trichloride and phenol can generate the gaseous substances such as hydrogen chloride after reacting, by fast the gaseous substances such as hydrogen chloride being removed by reactive distillation, adopt reactive distillation and magnetic stablizing bed coupling technique described in the present invention effectively can improve reaction rate, reduce the generation of side reaction.
Accompanying drawing explanation
Fig. 1 is present invention process flow chart
Marginal data: 1, Alkaline pretreatment device, 1-1, Alkaline pretreatment device external magnetic field control, 2, vavuum pump, 3, hydrogen pretreatment device, 4, reactive distillation and magnetic stablizing bed coupled reactor, 4-1, coupled reactor external magnetic field control, 5, coupled reactor circulating pump, 6, coupled reactor recirculation cooler, 7, magnetic separator, 7-1, magnetic separator external magnetic field control, 8, magnetic separator returns pump, 9, hydrogen chloride absorption tower, 10, coupled reactor overhead condenser
A, organic solvent, B, phosphorus trichloride, C, phenol, D, alkali lye, E, magnetic metal powder, F, nitrogen, G, hydrogen, H, reaction end gas 1, I, reaction end gas 2, J, watery hydrochloric acid, K, phosphite ester Metal complex catalysts
Detailed description of the invention
The technological means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below the specific embodiment of the present invention being described further, but not limiting protection scope of the present invention.
First for concrete operations flow process of the present invention, be illustrated by reference to the accompanying drawings:
Magnetic metal powder E is after Alkaline pretreatment device 1 cleans, by external magnetic field control 1-1, the magnetic metal powder E in alkali lye D is separated, send into hydrogen pretreatment device 3, by hydrogen G and nitrogen F to magnetic metal powder E process, reaction end gas 1H is discharged by vavuum pump 2, after process, oxygen content reaches target call not higher than 100ppm, sends into reactive distillation and magnetic stablizing bed coupled reactor 4.
Phosphorus trichloride B, phenol C, organic solvent A sends into reactive distillation and magnetic stablizing bed coupled reactor 4, magnetic metal powder E is from hydrogen pretreatment device 3, react in reactive distillation and magnetic stablizing bed coupled reactor 4, magnetic metal powder E is controlled dispersed by coupled reactor external magnetic field control 4-1, reaction heat is sent into coupled reactor recirculation cooler 6 by coupled reactor circulating pump 5 and is cooled, the reactant magnetic separator external magnetic field control 7-1 entered in magnetic separator 7 is separated magnetic metal powder E, magnetic metal powder E returns pump 8 by magnetic separator and returns to coupled reactor 4 circular response.Phosphite ester complex catalyst K is sent by magnetic separator 7 as product.Tower top material is refluxed by coupled reactor overhead condenser 10, and reacted hydrogen chloride gas is sent into hydrogen chloride absorption tower 9 absorption by overhead condenser 10 and made watery hydrochloric acid J, and reaction end gas 2I is discharged by hydrogen chloride absorption tower 9.
Embodiment 1:
15kg phenol C is added reactive distillation and magnetic stablizing bed coupled reactor 4.The phosphorus trichloride B of 6.63kg is delivered to reactive distillation and magnetic stablizing bed coupled reactor 4 by metering.Reactive distillation and magnetic stablizing bed coupled reactor 4 temperature are 160 DEG C, and pressure is 10KPa.The inlet amount of phosphorus trichloride B is 1.5l/h, and the circular flow of coupled reactor circulating pump 5 is 18l/h.Coupled reactor overhead condenser 10 temperature is 35 DEG C, and condensate liquid is back to tower top.After reaction 6h, sampling carries out gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B.
Add 4kg nickel powder E, the particle diameter of nickel powder is 30 microns, magnetic field intensity is 50KA/m, nickel powder E has carried out alkali cleaning at Alkaline pretreatment device 1 before adding reactor, 3% volume ratio hydrogen reducing and vacuum outgas at 420 DEG C in hydrogen pretreatment device 3, react in reactive distillation and magnetic stablizing bed coupled reactor 4, reactant is separated by magnetic separator 7, finally obtains phosphite ester Metal complex catalysts K.
The yield that reaction terminates rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester Metal complex catalysts K is not less than 98%.The main reactor volume space velocity of synthetic reaction is 0.3.
Embodiment 2:
15kg metacresol C is added reactive distillation and magnetic stablizing bed coupled reactor 4.The phosphorus trichloride B of 5.76kg is delivered to reactive distillation and magnetic stablizing bed coupled reactor 4 by metering.Reactive distillation and magnetic stablizing bed coupled reactor 4 temperature are 150 DEG C, and pressure is 30KPa.The inlet amount of phosphorus trichloride B is 1.5l/h, and the circular flow of coupled reactor circulating pump 5 is 30l/h.Coupled reactor overhead condenser 10 temperature is 35 DEG C, and condensate liquid is back to tower top.After reaction 10h, sampling carries out gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B.
Add 3kg nickel powder E, the particle diameter of nickel powder is 20 microns, magnetic field intensity is 50KA/m, nickel powder E has carried out alkali cleaning at Alkaline pretreatment device 1 before adding reactor, 3% volume ratio hydrogen reducing and vacuum outgas at heavy 420 DEG C of hydrogen pretreatment device 3, react in reactive distillation and magnetic stablizing bed coupled reactor 4, reactant is separated by magnetic separator 7, finally obtains phosphite ester Metal complex catalysts K.
The yield that reaction terminates rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester Metal complex catalysts K is not less than 98%.The main reactor volume space velocity of synthetic reaction is 0.2.
Embodiment 3:
20kg orthoresol C is added coupled reactor 4.The phosphorus trichloride of 7.68kg is delivered to reactive distillation and magnetic stablizing bed coupled reactor 4 by metering.Reactive distillation and magnetic stablizing bed coupled reactor 4 temperature are 220 DEG C, and pressure is 1KPag.The inlet amount of phosphorus trichloride B is 2l/h, and the circular flow of coupled reactor circulating pump 5 is 40l/h.Coupled reactor overhead condenser 10 temperature is 35 DEG C, and condensate liquid is back to tower top.After reaction 10h, sampling carries out gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B.
Add 3.5kg nickel powder E, the particle diameter of nickel powder is 10 microns, magnetic field intensity is 50KA/m, nickel powder E has carried out alkali cleaning at Alkaline pretreatment device 1 before adding reactor, 3% volume ratio reduction and vacuum outgas at 420 DEG C in hydrogen pretreatment device 3, react in reactive distillation and magnetic stablizing bed coupled reactor 4, reactant is separated by magnetic separator 7, finally obtains phosphite ester Metal complex catalysts K.
The yield that reaction terminates rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester Metal complex catalysts K is not less than 98%.The main reactor volume space velocity of synthetic reaction is 0.25.
Embodiment 4:
15kg paracresol C is added coupled reactor 4.The phosphorus trichloride of 6.3kg is delivered to reactive distillation and magnetic stablizing bed coupled reactor 4 by metering.Reactive distillation and magnetic stablizing bed coupled reactor 4 temperature are 220 DEG C, and pressure is 1KPag.The inlet amount of phosphorus trichloride B is 2l/h, and the circular flow of coupled reactor circulating pump 5 is 40l/h.Coupled reactor overhead condenser 10 temperature is 35 DEG C, and condensate liquid is back to tower top.After reaction 10h, sampling carries out gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B.
Add 3kg nickel powder E, the particle diameter of nickel powder is 5 microns, magnetic field intensity is 30KA/m, nickel powder E has carried out alkali cleaning at Alkaline pretreatment device 1 before adding reactor, 3% volume ratio reduction and vacuum outgas at 420 DEG C in hydrogen pretreatment device 3, react in reactive distillation and magnetic stablizing bed coupled reactor 4, reactant is separated by magnetic separator 7, finally obtains phosphite ester Metal complex catalysts K.
The yield that reaction terminates rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester Metal complex catalysts K is not less than 98%.The main reactor volume space velocity of synthetic reaction is 0.25.
Embodiment 5:
15kg naphthols C is added coupled reactor 4.The phosphorus trichloride of 4.75kg is delivered to reactive distillation and magnetic stablizing bed coupled reactor 4 by metering.Reactive distillation and magnetic stablizing bed coupled reactor 4 temperature are 220 DEG C, and pressure is 1KPag.The inlet amount of phosphorus trichloride B is 2l/h, and the circular flow of coupled reactor circulating pump 5 is 40l/h.Coupled reactor overhead condenser 10 temperature is 35 DEG C, and condensate liquid is back to tower top.After reaction 10h, sampling carries out gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B.
Add 2kg nickel powder E, the particle diameter of nickel powder is 10 microns, magnetic field intensity is 50KA/m, nickel powder E has carried out alkali cleaning at Alkaline pretreatment device 1 before adding reactor, 3% volume ratio reduction and vacuum outgas at 420 DEG C in hydrogen pretreatment device 3, react in reactive distillation and magnetic stablizing bed coupled reactor 4, reactant is separated by magnetic separator 7, finally obtains phosphite ester Metal complex catalysts K.
The yield that reaction terminates rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester Metal complex catalysts K is not less than 98%.The main reactor volume space velocity of synthetic reaction is 0.3.
Process of the present invention is described by specific embodiment.Those skilled in the art can use for reference the links such as the suitable feed change of content of the present invention, process conditions and realize other object corresponding, its relevant change does not all depart from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included within scope of the present invention.
Claims (8)
1. a reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling, it is characterized in that, configure phosphorus trichloride solution in organic solvent, and add phenol raw material, magnetic metal powder is added in the mixed solution containing phosphorus trichloride, phenol and organic solvent simultaneously; Reaction adopts reactive distillation to be coupled with magnetic stablizing bed, phosphorus trichloride and phenol generate single phosphite ester presoma by reactive distillation fast eliminating hydrogen chloride, simultaneously outside is forced magnetic field and is coupled with reactive distillation, form magnetic stable state, fully contact when magnetic metal powder is reacted with phosphite ester presoma, reactive distillation synthesizes single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling, described organic solvent is cycloalkane and aromatic hydrocarbon, and the addition of organic solvent makes phosphorus trichloride solubility in organic solvent not higher than 40% weight ratio.
2. a kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling according to claim 1, it is characterized in that, for prepare phenol, phosphorus trichloride, organic solution water content not higher than 100ppm.
3. a kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling according to claim 1, it is characterized in that, the mol ratio of described phenol and phosphorus trichloride is greater than 3:1, and wherein the mol ratio of phenol and phosphorus trichloride exceeds stoichiometry 10% mol ratio.
4. a kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling according to claim 1, and it is characterized in that, it is uniform magnetic field that magnetic field is forced in described outside, and magnetic field intensity is at 3-760KA/m.
5. a kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling according to claim 1, it is characterized in that, described magnetic metal powder comprises one or more mixing in iron powder, cobalt powder, nickel powder.
6. a kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling according to claim 1, it is characterized in that, described magnetic metal diameter of particle is 1 micron to 1000 microns, and metal-powder total oxygen is not higher than 100ppm.
7. a kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling according to claim 1, it is characterized in that, reactive distillation is 50-350 DEG C with the magnetic stablizing bed reaction temperature be coupled, and reaction pressure is-0.1MPaG-0.1MPaG.
8. a kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling according to claim 1, it is characterized in that, described reactive distillation makes the main reactor volume space velocity of synthetic reaction be not less than 0.1 with the magnetic stablizing bed technique of synthesizing single phosphite ester Metal complex catalysts that is coupled.
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| CN1493575A (en) * | 2002-10-28 | 2004-05-05 | 刘德亮 | Method of preparing phosphite ester |
| CN102050783A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Method for hydrofining caprolactam in magnetically stabilized bed |
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| US6759461B2 (en) * | 2002-07-17 | 2004-07-06 | Chung-Shan Institute Of Science & Technology | Phenolic phosphite antioxidants and polymer compositions containing said antioxidant |
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| CN1493575A (en) * | 2002-10-28 | 2004-05-05 | 刘德亮 | Method of preparing phosphite ester |
| CN102050783A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Method for hydrofining caprolactam in magnetically stabilized bed |
| CN103224529A (en) * | 2013-04-09 | 2013-07-31 | 天津市联瑞阻燃材料有限公司 | Preparation method of triphenyl phosphite |
| CN103232315A (en) * | 2013-04-11 | 2013-08-07 | 中国石油大学(华东) | A method for hydrogenation of benzene to prepare cyclohexane in a magnetically stabilized bed |
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