CN103801400A - Process for synthesizing mono-phosphite metal coordination catalyst by coupling reactive distillation and magnetically-stabilized bed - Google Patents
Process for synthesizing mono-phosphite metal coordination catalyst by coupling reactive distillation and magnetically-stabilized bed Download PDFInfo
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Abstract
The invention discloses a process for synthesizing a mono-phosphite metal coordination catalyst by coupling reactive distillation and a magnetically-stabilized bed. A phosphorus trichloride solution is mixed in an organic solvent, a phenol raw material is added, and magnetic metal powder is added into a mixed solution containing phosphorus trichloride, phenol and the organic solvent; reactive distillation and the magnetically-stabilized bed are coupled for reaction, phosphorus trichloride and phenol are reactively distilled to rapidly remove hydrogen chloride to generate a mono-phosphite precursor, and an externally magnetic field is applied to be coupled with reactive distillation to form a magnetically-stabilized state, so that the magnetic metal powder can fully contact with the mono-phosphite precursor during reaction to synthesize the mono-phosphite metal coordination catalyst by coupling reactive distillation and the magnetically-stabilized bed.
Description
Technical field
The invention belongs to Chemical Manufacture technology field, relate to particularly the technique of the synthetic single phosphite ester metal-complexing catalyst of a kind of reactive distillation and magnetic stablizing bed coupling.
Background technology
Metal-complexing catalyst is the solvay-type synthetic catalyst system of transition metal halide and organo-metallic compound composition, belongs to ligand complex structure.Refer to make by coordination the catalyst of reactant molecule activation.In this class catalyst, at least contain a metal ion or atom, no matter whether parent itself is complex compound, but in action time, catalytic active center is to occur with coordination structure, by changing metal-complexing number or dentate, the rarest a kind of reaction molecular enters co-ordination state and is activated, thereby promotes the carrying out of reaction.Homogeneous complex catalysis agent can melt into homogeneous phase in reaction system complex compound catalyst.Majority is the salt of metallo-organic compound, transition metal, complex compound catalyst that can melt into homogeneous phase in reaction system.Prepare easier, earlier in industrial application.As Ziegler catalyst (titanium tetrachloride-alkyl aluminum), the Ziegler-Natta catalyst (titanium trichloride-alkyl aluminum) of alkene in rhodium catalyst, the olefinic polyreaction of the palladium catalyst of the cobalt carbonyl catalyst of the cobalt carbonyl catalyst of the synthetic aldehyde processed of carbonyl, phosphine-modified and rhodium carbonyl catalyst, ethylene acetaldehyde processed, Production of Acetic Acid by Methanol Carbonylation, the Raney nickel in conjugated alkene cyclization etc.
Phosphite ester metallic catalyst belongs to the one that metal coordinates complex catalyst, is reacted and obtains with metal precursor by phosphite ester.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 synthesizing for hydrocyanation reaction catalyst system and catalyzing organophosphor metal complex.Can have important effect to hydroformylation reaction and cyanogenation because phosphite ester metal coordinates complex catalyst (phosphorous acid cobalt, phosphorous acid nickel), therefore phosphorous acid metallic catalyst causes extensive attention.In formylation reaction, wherein bis-phosphite metallic catalyst can have larger sterically hinderedly compared with triphenyl phosphorus, adopts phosphite ester can effectively improve the selective of formylation reaction.In adiponitrile reaction, patent CN101479237A, in CN101484417A, by the hydrocyanation technique of butadiene, a kind of bidentate phosphites part and multidentate phosphite catalyst can be converted into butadiene allyl acetonitrile and adiponitrile.But the technological process for 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 coordination metals such as iron, cobalt, nickel have stronger magnetic characteristic in single phosphite ester production process, combine magnetic stablizing bed mode of being combined with magnetic metal powder and carry out monodentate phosphite complex catalyst and have not been reported.During traditional handicraft is synthetic, 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 liquid-solid separation.
Summary of the invention
The present invention is for better solving the problems of the technologies described above, consider iron in single phosphite catalysts production process, cobalt, the coordination raw metals such as nickel have stronger magnetic characteristic, the technique of the synthetic single phosphite ester metal-complexing catalyst of a kind of reactive distillation and magnetic stablizing bed coupling is provided, magnetic stablizing bed traditional mechanical agitation and the filtration centrifugal separation process fluid bed of being different from, when making reactive distillation, the technique of employing reactive distillation and magnetic stablizing bed coupling also carries out take magnetic-particle as solid phase, the magnetic current of magnetic-particle under additional magnetic fields, solid particle in bed is not to do unordered freely-movable in operating process, but be ordered arrangement state.Magnetic stablizing bed can stable operation in wider scope, magnetic metal powder is dispersed in reactor uniformly, can improve interphase mass transfer.The concrete technical scheme adopting is as follows:
The technique of the synthetic single phosphite ester metal-complexing catalyst of a kind of reactive distillation and magnetic stablizing bed coupling, in organic solvent, configure phosphorus trichloride solution, and add phenol raw material, magnetic metal powder is added in the mixed solution that contains phosphorus trichloride, phenol and organic solvent simultaneously; Reaction adopts reactive distillation and magnetic stablizing bed coupling, phosphorus trichloride and phenol generate single phosphite ester presoma by reactive distillation fast eliminating hydrogen chloride, magnetic field and reactive distillation coupling are forced in outside simultaneously, form magnetic stable state, when magnetic metal powder is reacted with phosphite ester presoma, fully contact, single phosphite ester metal-complexing catalyst is synthesized in reactive distillation and magnetic stablizing bed coupling.
For the water content of the phenol prepared, phosphorus trichloride, organic solution 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.
A mole proportioning for described phenol and phosphorus trichloride is greater than 3:1, and wherein a mole proportioning for 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.
The reaction temperature of reactive distillation and magnetic stablizing bed coupling is 50-350 ℃, and reaction pressure is-0.1MPaG-0.1MPaG.
The technique of the synthetic single phosphite ester metal-complexing catalyst of described reactive distillation and magnetic stablizing bed coupling makes the main reactor volume space velocity of synthetic reaction be not less than 0.1.
In the preparation technology of single phosphorous acid esters metal-complexing catalyst of a kind of reactive distillation of the present invention and magnetic stablizing bed coupling, described phenol can be metacresol, orthoresol, paracresol, phenol, naphthols, anthrol.
The organic solvent adding is cycloalkane and aromatic hydrocarbon and combination, can select cyclohexane, benzene and toluene, phosphorus trichloride, excessive phenol are dispersed in organic solvent, on the one hand owing to there being higher dispersiveness, the addition that guarantees 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 guarantees that phosphorus trichloride has higher conversion ratio simultaneously; On the other hand, because the reacting phase of phosphorus trichloride and phenol is worked as acutely, attenuating reactant concentration makes to respond dangerous controlled in state, and it is out of control that inhibitory reaction is acutely avoided.The methods such as described phenol, phosphorus trichloride, organic solvent raw material need adopt refining way, and process for purification comprises employing rectifying, absorption, need control not higher than 100ppm for the water content of the phenol prepared, phosphorus trichloride, organic solvent.
Simultaneously, magnetic metal powder is added in the mixed solution that contains phosphorus trichloride, phenol and organic solvent, in reactive distillation column, force the coupling of magnetic field and reactive distillation by outside, combine reactive distillation and magnetic stablizing bed advantage, on the one hand, magnetic metal powder forms magnetic stable state, to guarantee that magnetic metal powder fully contacts with phosphorous acid presoma, regulate uniform magnetic field intensity at 3-760KA/m, guarantee that nickel powder forms the stable orderly suspended state of magnetic; On the other hand, the raw materials such as phosphorus trichloride and phenol generate the hydrogen chloride generating in phosphite ester process and remove fast by reactive distillation, can improve the synthetic speed of single phosphite ester metal-complexing catalyst.Reactive distillation and magnetic stablizing bed coupling technique have also been accelerated reaction rate, make the main reactor volume space velocity of single phosphite ester metal-complexing catalyst reaction be not less than 0.1, volume space velocity is defined as unit volume reactor can process the volume that makes phosphorus trichloride transform the single phosphite ester of generation completely.It is 0.01 even lower that the volume space velocity of similar reaction is generally.Rectifying column adopts plate column, and sieve tray avoids solid metal powder to stop up rectifying column, and reaction tower tower reactor reactor adopts magnetic stablizing bed strengthening.Tower reactor discharging increases magnetic separator, metal powder particle in interception discharging, avoided the technique such as recoil, cleaning of traditional handicraft middle filtrator and cyclone hydraulic separators, and in traditional liquid, unreacted solid metal powder utilizes metallic filter, ceramic filter, cyclone hydraulic separators to carry out liquid-solid 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 of reaction.Meanwhile, for guaranteeing that powder total oxygen is not higher than 100ppm, magnetic metal powder need to be considered vacuum outgas, and the techniques such as surface treatment are strictly controlled oxygen content.On the one hand, hydrogen reducing and vacuum outgas are key factors that reduces metal powder oxygen content, and reduction temperature is not less than 400 ℃ conventionally, add in magnetically stabilized bed reactor after metal powder is degassed fast and react.The pretreated way of magnetic metal powder also comprises alkali cleaning, the alkali cleaning of indication need to remove the grease on magnetic metal powder surface, alkali lye comprises the highly basic such as NaOH, potassium hydroxide, or the weak base such as calcium hydroxide, ungrease treatment is carried out in powder granule surface, effectively improve magnetic stablizing bed reaction efficiency.
The reaction temperature of reactive distillation and magnetic stablizing bed coupling is 50-350 ℃, and suitable temperature range is also conducive to the carrying out of reaction, conventionally selects 160-220 ℃.Reaction pressure is-0.1MPaG-0.1MPaG.Reactive distillation is in negative pressure, and the hydrogen chloride that is conducive to reaction generation removes fast from reaction system.
Meanwhile, adopt reactive distillation and magnetic stablizing bed coupling technique can effectively 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-complexing catalyst is not less than 95%.
The additional controlling magnetic field of coupled reactor 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 obstruction is attached on wall and interior panelling, and magnetic presents ordered arrangement, and magnetic powder gap is even, is not easy to produce channel, reaction efficiency improves.And follow-up lock out operation easily by magnetic metal powder preferably by magnetic stalling characteristic, simplified operating process, reduced running cost.And the reactants such as phosphorus trichloride can generate the gaseous substances such as hydrogen chloride after reacting with phenol, by can fast the gaseous substances such as hydrogen chloride being removed by reactive distillation, adopt reactive distillation described in the present invention and magnetic stablizing bed coupling technique can effectively improve reaction rate, reduce the generation of side reaction.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention
Marginal data: 1, Alkaline pretreatment device, 1-1, the additional controlling magnetic field of Alkaline pretreatment device, 2, vavuum pump, 3, hydrogen pretreatment device, 4, reactive distillation and magnetic stablizing bed coupled reactor, 4-1, the additional controlling magnetic field of coupled reactor, 5, coupled reactor circulating pump, 6, coupled reactor recirculation cooler, 7, magnetic separator, 7-1, the additional controlling magnetic field of magnetic separator, 8, magnetic separator returns to 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-complexing catalyst
The specific embodiment
For technological means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below the specific embodiment of the present invention is described further, but does not limit 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 additional controlling magnetic field 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, magnetic metal powder E is processed, reaction end gas 1H discharges by vavuum pump 2, after processing, 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 is sent into reactive distillation and magnetic stablizing bed coupled reactor 4, magnetic metal powder E is from hydrogen pretreatment device 3, react with magnetic stablizing bed coupled reactor 4 at reactive distillation, control magnetic metal powder E by the additional controlling magnetic field 4-1 of coupled reactor dispersed, it is cooling that reaction heat is sent into coupled reactor recirculation cooler 6 by coupled reactor circulating pump 5, the additional controlling magnetic field 7-1 of magnetic separator that reactant enters in magnetic separator 7 separates magnetic metal powder E, magnetic metal powder E returns to pump 8 by magnetic separator and returns to coupled reactor 4 circular responses.Phosphite ester complex catalyst K is sent by magnetic separator 7 as product.Tower top material refluxes by coupled reactor overhead condenser 10, and reacted hydrogen chloride gas is sent into 9 absorptions of hydrogen chloride absorption tower by overhead condenser 10 and made watery hydrochloric acid J, and reaction end gas 2I discharges by hydrogen chloride absorption tower 9.
Embodiment 1:
15kg phenol C is added to 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 ℃, 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 are 35 ℃, and condensate liquid is back to tower top.After reaction 6h, gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B are carried out in sampling.
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 adding before reactor, 3% volume ratio hydrogen reducing and vacuum outgas at 420 ℃ in hydrogen pretreatment device 3, react with magnetic stablizing bed coupled reactor 4 at reactive distillation, reactant separates by magnetic separator 7, finally obtains phosphite ester metal-complexing catalyst K.
The yield that reaction finishes rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester metal-complexing catalyst 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 to 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 ℃, 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 are 35 ℃, and condensate liquid is back to tower top.After reaction 10h, gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B are carried out in sampling.
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 adding before reactor, 3% volume ratio hydrogen reducing and vacuum outgas at heavy 420 ℃ of hydrogen pretreatment device 3, react with magnetic stablizing bed coupled reactor 4 at reactive distillation, reactant separates by magnetic separator 7, finally obtains phosphite ester metal-complexing catalyst K.
The yield that reaction finishes rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester metal-complexing catalyst 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 to 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 ℃, 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 are 35 ℃, and condensate liquid is back to tower top.After reaction 10h, gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B are carried out in sampling.
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 adding before reactor, 3% volume ratio reduction and vacuum outgas at 420 ℃ in hydrogen pretreatment device 3, react with magnetic stablizing bed coupled reactor 4 at reactive distillation, reactant separates by magnetic separator 7, finally obtains phosphite ester metal-complexing catalyst K.
The yield that reaction finishes rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester metal-complexing catalyst 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 to 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 ℃, 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 are 35 ℃, and condensate liquid is back to tower top.After reaction 10h, gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B are carried out in sampling.
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 adding before reactor, 3% volume ratio reduction and vacuum outgas at 420 ℃ in hydrogen pretreatment device 3, react with magnetic stablizing bed coupled reactor 4 at reactive distillation, reactant separates by magnetic separator 7, finally obtains phosphite ester metal-complexing catalyst K.
The yield that reaction finishes rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester metal-complexing catalyst 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 to 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 ℃, 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 are 35 ℃, and condensate liquid is back to tower top.After reaction 10h, gas chromatographic analysis, the conversion ratio 100% of phosphorus trichloride B are carried out in sampling.
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 adding before reactor, 3% volume ratio reduction and vacuum outgas at 420 ℃ in hydrogen pretreatment device 3, react with magnetic stablizing bed coupled reactor 4 at reactive distillation, reactant separates by magnetic separator 7, finally obtains phosphite ester metal-complexing catalyst K.
The yield that reaction finishes rear phosphite ester presoma is not less than 97%, and the yield of phosphite ester metal-complexing catalyst 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 content appropriate change raw material of the present invention, process conditions and realize corresponding other object, its relevant change does not all depart from content of the present invention, within all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included in scope of the present invention.
Claims (9)
1. the technique of the synthetic single phosphite ester metal-complexing catalyst of a reactive distillation and magnetic stablizing bed coupling, it is characterized in that, in organic solvent, configure phosphorus trichloride solution, and add phenol raw material, magnetic metal powder is added in the mixed solution that contains phosphorus trichloride, phenol and organic solvent simultaneously; Reaction adopts reactive distillation and magnetic stablizing bed coupling, phosphorus trichloride and phenol generate single phosphite ester presoma by reactive distillation fast eliminating hydrogen chloride, magnetic field and reactive distillation coupling are forced in outside simultaneously, form magnetic stable state, when magnetic metal powder is reacted with phosphite ester presoma, fully contact, single phosphite ester metal-complexing catalyst is synthesized in reactive distillation and magnetic stablizing bed coupling.
2. the technique of the synthetic single phosphite ester metal-complexing catalyst of a kind of reactive distillation and magnetic stablizing bed coupling according to claim 1, is characterized in that, for the water content of the phenol prepared, phosphorus trichloride, organic solution not higher than 100ppm.
3. the technique that single phosphite ester metal-complexing catalyst is synthesized in a kind of reactive distillation and magnetic stablizing bed coupling according to claim 1, it is characterized in that, 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.
4. the technique that single phosphite ester metal-complexing catalyst is synthesized in a kind of reactive distillation and magnetic stablizing bed coupling according to claim 1, it is characterized in that, a mole proportioning for described phenol and phosphorus trichloride is greater than 3:1, and wherein a mole proportioning for phenol and phosphorus trichloride exceeds stoichiometry 10% mol ratio.
5. the technique that single phosphite ester metal-complexing catalyst is synthesized in a kind of reactive distillation and magnetic stablizing bed coupling according to claim 1, is characterized in that, described high-intensity magnetic field is uniform magnetic field, and magnetic field intensity is at 3-760KA/m.
6. the technique that single phosphite ester metal-complexing catalyst is synthesized in a kind of reactive distillation and magnetic stablizing bed coupling according to claim 1, is characterized in that, described magnetic metal powder comprises one or more mixing in iron powder, cobalt powder, nickel powder.
7. the technique that single phosphite ester metal-complexing catalyst is synthesized in a kind of reactive distillation and magnetic stablizing bed coupling according to claim 1, 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.
8. the technique that single phosphite ester metal-complexing catalyst is synthesized in a kind of reactive distillation and magnetic stablizing bed coupling according to claim 1, it is characterized in that, the reaction temperature of reactive distillation and magnetic stablizing bed coupling is 50-350 ℃, and reaction pressure is-0.1MPaG-0.1MPaG.
9. the technique that single phosphite ester metal-complexing catalyst is synthesized in a kind of reactive distillation and magnetic stablizing bed coupling according to claim 1, it is characterized in that, the technique of the synthetic single phosphite ester metal-complexing catalyst of described reactive distillation and magnetic stablizing bed coupling makes the main reactor volume space velocity of synthetic reaction be not less than 0.1.
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| CN112791680A (en) * | 2020-12-24 | 2021-05-14 | 华阳新材料科技集团有限公司 | A nickel phosphorus complex synthesis system for adiponitrile production |
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| US20040014852A1 (en) * | 2002-07-17 | 2004-01-22 | Chung-Shan Institute Of Science & Technology | Phenolic phosphite antioxidants and polymer compositions containing said antioxidant |
| CN1493575A (en) * | 2002-10-28 | 2004-05-05 | 刘德亮 | Method of preparing phosphite ester |
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