CN1288777A

CN1288777A - Membrane reactor

Info

Publication number: CN1288777A
Application number: CN 99120815
Authority: CN
Inventors: 熊国兴; 刘百军; 潘秀莲; 盛世善; 杨维慎; 刘杰
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 1999-09-22
Filing date: 1999-09-22
Publication date: 2001-03-28
Anticipated expiration: 2019-09-22
Also published as: CN1128008C

Abstract

The film reactor comprises ceramic film and shell body, which is characterized by that the described ceramic film is a tubular body whose one end is closed, said ceramic film is used as support, the catalyst can be distributed on the surface of inside and/or outside and in channel, said shell body possesses inlet and outlet which are included in external portion of said ceramic film, and a stirring device is placed in the interior of said ceramic film. Said invention is specially applicable to selective hydrogenation reaction of alpha and beta-unsaturated oxo-compound, at the same time of ensuring production of alpha and beta-unsaturated alcohol, it can quicken reaction speed, make the reaction implement under the moderate condition, and can avoid the specific requirements of high pressure reaction for reactor.

Description

A kind of membrane reactor

The present invention relates to chemical reactor, a kind of novel membrane reactor specifically is provided, it is specially adapted to α, and beta-unsaturated carbonyl compound is selected hydrogenation system α, beta unsaturated alcohol.

United States Patent (USP) (US Pat.4 179 470,1979) use Pd-Ru (92-97%:8-3%) membrane reactor of selective permeation hydrogen with manufacturing process of aniline through nitrobenzene hydrogenation, it is divided into two Room with barrier film with reactor, and reactant sucks with pump from one side of film, and the product behind hydrogenation leaves; And H2 adds from another chamber, through film diffusion, activation, combines with reactant again, has improved the concentration of hydrogen effectively, the carrying out of accelerated reaction.In addition, this reactor also is used for the selective hydrogenation of acetylene compound, alkadienes, owing to use metal Pd, metal Pd is very strong to the activation capacity of the two keys of C=C, so this reactor is not suitable for and α, the selective hydrogenation reaction of beta-unsaturated carbonyl compound.Naganoto (Chem Eng.Commun, 34 (1985) 315-325) be a thickness that 50 microns fine and close Pd flat sheet membrane separates, become two chambers, each chamber has an injection port and an outlet, one of them chamber air inlet phase reaction thing, hydrogen is advanced in another chamber, hydrogen is with the side direction opposite side diffusion from film of the mechanism of dissolving diffusion, on the surface of another side form is to exist with atomic state H, the reactivity of this atomic state H is far above Gaseous Hydrogen, this reactor has been used for ethylene hydrogenation, propylene, and the hydrogenation reaction of 1-butylene, the dense palladium film that it is used is though can 100% selection see through hydrogen, but it is too big to prepare the used noble metal consumption of this film, the more important thing is that the separating area that this film has is too little.European patent European Patent Application 0 293 186 is with palldium alloy control curl, be assembled into membrane reactor, be used for the liquid-phase hydrogenatin reaction, hydrogen sees through film and diffuses to reaction zone, the speed of phenylacetylene hydrogenation reaction is directly with hydrogen 10 times with the reaction of bubbling form, cinnamic selectivity is up to 92%, the pilot scale of this reactor, operating condition has arrived 973K, pressure 10MPa is though with palldium alloy control curl, increased effective separating area of film effectively, but the consumption of noble metal is not resolved yet, will strengthen production cost.The membrane reactor of Gobina developments such as (J.Mem.Sci.90 (1994) 11-19) is to be counterdie with the tubulose porous ceramic film, being coated with last layer thick with sputtering technology is 6 microns, fine and close Pd-Ag alloy film, this reactor is used for the ethane dehydrogenation reaction, reacts required catalyst P d/Al ₂O ₃Be filled in the film pipe, the shell side shifts out conversion zone with inert gas purge with the hydrogen that adds the fast response generation, because hydrogen constantly is moved out of reaction zone, originally the dehydrogenation conversion and the selectivity that are subjected to thermodynamics equilibrium limit are all increased substantially, the membrane reactor of being reported is a counterdie with the tubulose porous ceramic film then, being coated with last layer thick with sputtering technology is 6 microns, fine and close Pd-Ag alloy film, reduced the consumption of noble metal, but technology of preparing with existing metal film, on porous ceramics or metal counterdie, prepare not have and split the metallic film that lacks no pinprick, be still a problem that awaits research and development, metal Pd is also inapplicable to the selective hydrogenation reaction that the present invention relates to simultaneously.

The object of the present invention is to provide a kind of novel membrane reactor, it is specially adapted to α, the beta-unsaturated carbonyl compound selective hydrogenation reaction, guaranteeing to generate α, in the time of beta unsaturated alcohol, fast reaction speed makes to be reflected under the comparatively gentle condition and carries out, and avoids the specific (special) requirements of reaction under high pressure to reactor.

The invention provides a kind of membrane reactor, constitute by ceramic membrane (1) and housing (2), it is characterized in that: described ceramic membrane (1) is the tubular body of bottom sealing, makes carrier with ceramic membrane, and catalyst distribution is in the surface and duct in the inboard of ceramic membrane and/or the outside; Housing (2) has import and export (21) (22), and its inclusion is in the outside of ceramic membrane (1); Agitator (3) is arranged at the inside of ceramic membrane (1).

Membrane reactor provided by the present invention is the carrier of catalyst with the porous ceramic film of an end closure, the catalytic active layer distribution is the one or both sides of ceramic-film tube, hydrogen and liquid phase reactor thing are respectively from the both sides sample introduction of film pipe, because the effect of capillary force, liquid phase reactor thing molecular diffusion to catalytic active layer contacts with hydrogen on being adsorbed on catalytic active site, and react, by control Hydrogen Vapor Pressure and flow, and the flow of liquid phase reactor thing, can regulate the contact-making surface of gas-liquid two-phase, and time of contact, and the distribution of the reactant concentration in the catalytic active layer, thereby reactive activity and selectivity are improved, the characteristics of this reactor are the resistance to mass tranfers that has reduced in traditional phase reaction, be hydrogen molecule to arrive catalyst surface must be through surrounding one deck liquid film and the intergranular resistance to mass tranfer of catalyst granules, and intergranular resistance to mass tranfer, reduced the energy consumption in traditional heterogeneous catalytic reaction, improved the contact area of gas phase and liquid phase reactor thing molecule effectively, and surperficial hydrogen concentration can control by regulating the hydrogen dividing potential drop, can several times in addition tens times of ground improve the speed and the hydrogenation selectivity of hydrogenation reactions.Because the present invention adopts this special structural design, makes it be specially adapted to the situation that reactant is liquid and gas, when being used for α, beta-unsaturated carbonyl compound selection hydrogenation system α, during beta unsaturated alcohol, the matrix of used tubular ceramic film is Al ₂O ₃Or SiO ₂Asymmetric perforated membrane, teleblem aperture are the 2-50 micron; Catalyst is main active component with Co, and so that one or more are the auxiliary activity composition among Pt, Pd, Rh, Ru, Ir, the Os, the amount of Co accounts for 5-50%wt, and the amount of noble metal accounts for 0.0001-0.25%wt.

The preparation of used ceramic membrane can adopt the Sol-gel technology to make the catalyst activity component be distributed in the inboard and/or the outside of film pipe among the present invention.

In addition, at preparation α, when beta-unsaturated carbonyl compound is selected the hydrogenation membrane reactor, with CoCl ₂, Co (NO ₃) ₂, Co (OAc) ₂Being the presoma of Co, is the presoma of noble metal with chloride, nitrate, the carbonyls of Pt, Pd, Rh, Ru, Ir, Os; The good film pipe of dip-coating is dry 2-20 hour of 300-450K, 500-900K roasting 1-30 hour.The film pipe that roasting is good activates 0.5-20 hour in the hydrogen stream under the 500-900K temperature, hydrogen flow rate is 10-100ml/min.It is necessary for the diffusion rate of accelerating hydrogen film being carried out suitable activation, and membrane reactor is used for α, and beta-unsaturated carbonyl compound is selected hydrogenation system α, beta unsaturated alcohol, reaction temperature 298-423K, oxygen pressure 0.01-0.5MPa.

Below by accompanying drawing in detail the present invention is described in detail.

Accompanying drawing 1 is the membrane reactor schematic diagram.

Embodiment 1.

Tubulose α-the Al of opening at one end ₂O ₃On the outer surface of ceramic membrane, use sol-gal process, the dip-coating last layer is thick to be the γ-Al of 8 micron thickness ₂O ₃Film, and support active component Co and Pt, its ratio is 100: 5.The good film pipe of dip-coating under 300K dry 5 hours, roasting is 10 hours under 700K.The film pipe that roasting is good reduced 6 hours in the hydrogen stream of 700K, and hydrogen flow rate is 20ml/min.At the membrane reactor of forming by this film pipe 15.1 * 10 ^-4, and the TOF value on the traditional catalyst is 2.5 * 10 ⁴Mole cinnamic acid/mole cobalt * s.

Claims

1. membrane reactor is made of ceramic membrane (1) and housing (2), and it is characterized in that: described ceramic membrane (1) is the tubular body of bottom sealing, makes carrier with ceramic membrane, and catalyst distribution is in the surface and duct in the inboard of ceramic membrane and/or the outside; Housing (2) has import and export (21) (22), and its inclusion is in the outside of ceramic membrane (1); Agitator (3) is arranged at the inside of ceramic membrane (1).

2. according to the described membrane reactor of claim 1, it is characterized in that: the matrix of used tubular ceramic film is Al ₂O ₃Or SiO ₂Asymmetric perforated membrane, teleblem aperture are the 2-50 micron; Catalyst is main active component with Co, and so that one or more are the auxiliary activity composition among Fr, Pd, Rh, Ru, Ir, the Os, the amount of Co accounts for 5-50%wt, and the amount of noble metal accounts for 0.0001-0.25%wt.

3. the preparation method of a claim 1,2 described membrane reactors is characterized in that: adopt the Sol-gel technology to make the catalyst activity component be distributed in the inboard and/or the outside of film pipe.

4. according to the preparation method of the described membrane reactor of claim 3, it is characterized in that: with CoCl ₂, Co (NO ₃) ₂, Co (OAc) ₂Being the presoma of Co, is the presoma of noble metal with chloride, nitrate, the carbonyls of Pt, Pd, Rh, Ru, Ir, Os; The good film pipe of dip-coating is dry 2-20 hour of 300-450K, 500-900K roasting 1-30 hour.

5. according to the preparation method of the described membrane reactor of claim 4, it is characterized in that: the film pipe that roasting is good activates 0.5-20 hour in the hydrogen stream under the 500-900K temperature, hydrogen flow rate is 10-100ml/min.

6. claim 1,2 described membrane reactors are used for α, and beta-unsaturated carbonyl compound is selected hydrogenation system α, beta unsaturated alcohol, reaction temperature 298-423K, Hydrogen Vapor Pressure 0.01-0.5MPa.