CN104709921A - Micro-channel reactor and method applying micro-channel reactor to produce magnetic titanium silicalite - Google Patents
Micro-channel reactor and method applying micro-channel reactor to produce magnetic titanium silicalite Download PDFInfo
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- CN104709921A CN104709921A CN201510106554.4A CN201510106554A CN104709921A CN 104709921 A CN104709921 A CN 104709921A CN 201510106554 A CN201510106554 A CN 201510106554A CN 104709921 A CN104709921 A CN 104709921A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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Abstract
The invention provides a micro-channel reactor and a method applying the micro-channel reactor to produce a magnetic titanium silicalite. The novel micro-channel reactor is designed by analyzing and calculating the fluid field distribution of the reactor, and adopts a secondary micro-channel structure. A static grinding disc inner chamber of the reactor is provided with secondary reducing diameters of opposite directions; the upper reducing diameter of the static grinding disc inner chamber and the outer wall of a falling film cylinder form a primary falling film micro-channel; the lower reducing diameter of the static grinding disc inner chamber and the outer side wall of a movable grinding disc form a secondary react micro-channel. Two kinds of solution entering the reaction vessel are conducted by compulsive micro mixing instantly in the reactor; small seed crystals are generated at a high speed, and are conducted by adsorption regrowth on magnetic nanometer particles to obtain the magnetic loading modified titanium silicalite eventually; catalyst performance is improved remarkably.
Description
Technical field
The invention belongs to Catalyst Production technical field, especially relate to a kind of micro passage reaction and use the method for its production Magnetic titanium silicon molecular sieve.
Background technology
Transition metals Ti is introduced to have in the framework of molecular sieve of ZSM-5 structure and forms a kind of novel titanosilicate with excellent directional catalyzing oxidation susceptibility.It not only has the catalysed oxidn of titanium, and the shape of selecting with ZSM-5 acts on and excellent stability, oxidisability, and specific selectivity.Take HTS as catalyzer, the low-temperature catalyzed system of green that forms for oxygenant of hydrogen peroxide, can the multiple organic compound of catalyzed oxidation in a mild condition, the hydroxylation of such as phenol and aromatic hydrocarbons, alkene epoxidation, ketone are oximes, the partial oxidation etc. of amine and saturated alkane, and in these reactions, HTS all shows good reactive behavior and selectivity.Particularly the catalyst system that forms of TS-1 and hydrogen peroxide, avoids the problem of complex process and environmental pollution, has good prospects for commercial application.
Titanium-silicon molecular sieve TS-1 is considered to the milestone in 20th century molecular sieve catalytic eighties field, since taking titanium-silicon molecular sieve TS-1 as catalyzer, and H
2o
2after the cyclohexanone oxamidinating technique of oxygenant successfully developed in 1986, many scholars and the mechanism Ammoximation reaction to pimelinketone has done large quantifier elimination and improvement.Cyclohexanone-oxime is the important intermediate preparing hexanolactam, and hexanolactam, except being mainly used in fiber, engineering plastics, food packaging film, is also widely used in fields such as electronic component, medical article, daily necessities and industrial machineries; Along with social process of industrialization is constantly accelerated, day by day increase in the demand of Chinese hexanolactam, built up the oximes full scale plant of many covers different scales so far at home.China's sky occasion have also carried out a series of research to the oximes legal system of use for the novel process of cyclohexanone-oxime, on the basis of lab scale, pilot scale, established the oximes device of a set of 200kt/a titanium molecular sieve catalysis pimelinketone in 2014, this is a set of oximes full scale plant that Chinese sky occasion are applied China's technology of having by oneself and independently built.The recycle section of Ammoximation reaction rear catalyst adopts unconventional membrane separation process, HTS particle and the long-time high frequency friction of ceramic-film tube inwall, although strictly limit the flow velocity of ceramic membrane liquid in pipe when filtering, the glutinous wall of HTS and wearing and tearing cannot be avoided to run off.From oximes plant running situation domestic at present, all there is the place that some are to be modified.Especially, the titanium-silicon molecular sieve catalyst particle size that Ammoximation reaction uses is too tiny, and reaction product need be transported to the separation carrying out catalyzer in filtration unit, and filtration unit needs high frequency recoil regeneration, the processing load of filtering system is large, and the turnaround is short, causes start-stop car frequency high.
Traditional technology mainly utilizes tank reactor to prepare molecular sieve, the mixing of liquid-liquid diphase is realized by the mode stirred, mixing space is whole stirring tank, time several to tens hours, be subject to concentration gradient restriction, speed of reaction and velocity of diffusion slowly, mix very insufficient, easily there is dephasign in reaction process, limit the catalytic performance of material.In order to ensure the efficiency utilization of catalyzer and be separated convenient, carry out innovating and improving from catalytic material and production method, oximes technique will be optimized from source, promote and produce load.
Summary of the invention
In view of this, the present invention is intended to propose a kind of micro passage reaction, to realize the Rapid contact of fluid, mixes and react within the extremely short time, thus preparing efficient HTS.
For achieving the above object, technical scheme of the present invention is achieved in that a kind of micro passage reaction, comprise capping, shell of reactor and reactor base, described shell of reactor is fixed on reactor base, is provided with motor in described shell of reactor, and described motor is connected with turning axle, and described turning axle is provided with movable grinding disc, movable grinding disc outer race is equipped with static cutting disk, and static cutting disk is arranged on the inwall of shell of reactor, and capping is arranged on above static cutting disk; Described capping is provided with a feed duct and falling liquid film cylinder, and feed duct is positioned at the inside of falling liquid film cylinder, is provided with spraying gun bottom a described feed duct; Described capping is provided with No. two feed duct, and described No. two feed duct are between falling liquid film cylinder and static cutting disk; Be provided with tapping channel between described movable grinding disc and reactor base, be provided with discharging propeller runner in described tapping channel, and described shell of reactor is provided with discharging supply pipe, described tapping channel is corresponding with the position of discharging supply pipe; Preferably, in described static cutting disk, be provided with cooling channel, described cooling channel be connected with import and the outlet of circulating cooling medium; Preferably, described turning axle is provided with sealing member through the position of tapping channel; Preferably, bottom described movable grinding disc, be provided with discharging propeller runner, be fixed on movable grinding disc or turning axle, and impeller is open type or semi-enclosed.
Preferably, described static cutting disk inner chamber has secondary reducing, and from top to bottom, diameter successively decreases upper part of described static cutting disk gradually, is top reducing; From top to bottom, diameter increases progressively lower part of static cutting disk gradually, is bottom reducing; And the top reducing of described static cutting disk inner chamber and falling liquid film drum outer wall form the falling liquid film microchannel of the first step, static cutting disk inner chamber bottom reducing and movable grinding disc outer side surface form the microchannel of the second stage; Movable grinding disc is up-thin-low-thick " loudspeaker " type structure, corresponding with the bottom reducing wall configuration of static cutting disk; Preferably, the tapering of the top reducing of described static cutting disk inner chamber is 3 ~ 60 °; The radian of the outer wall circular arc of described movable grinding disc is 10 ~ 80 °.
Described tapering be static cutting disk inner chamber longitudinal axes tangent plane on the angle of hypotenuse and vertical direction; Described radian is the radian of movable grinding disc longitudinal axes tangent plane upper side edge.
Feed duct lower end connects spraying gun, and the drop size that spraying gun is formed is 200 ~ 1200 microns, and the ring-type liquid band that spraying gun is formed is ejected on the liquid film that static cutting disk top reducing and falling liquid film cylinder formed.
Preferably, also comprise main regulation dish and auxiliary adjustment disk, described main regulation dish is arranged between shell of reactor and capping; Described auxiliary adjustment disk is arranged on capping top, and corresponding with the position of falling liquid film cylinder.
The falling liquid film microchannel that the wall of static cutting disk inner chamber top reducing and falling liquid film drum outer wall are formed, its size can modulation, the size range of falling liquid film microchannel outlet is 10 ~ 1000 microns, and the relative position that the gap length of falling liquid film microchannel outlet changes falling liquid film cylinder and static cutting disk by auxiliary adjustment disk realizes.Auxiliary adjustment disk is arranged on capping top, realizes controlling by adjusting bolt or screw thread;
Microchannel between the wall of static cutting disk inner chamber bottom reducing and movable grinding disc outer wall, its size can modulation, the size range of microchannel thickness is 10 ~ 1000 microns, and the relative position that channel thickness changes movable grinding disc and static cutting disk by main regulation dish realizes.Main regulation dish is arranged between shell of reactor and capping, realizes controlling by adjusting bolt or screw thread.
Preferably, the teeth groove that the wall of described static cutting disk inner chamber bottom reducing all has arrangement mode different from movable grinding disc outer side surface, preferably, teeth groove is twill, radial direction or spirrillum.
Another object of the present invention is to propose a kind of method using micro passage reaction production Magnetic titanium silicon molecular sieve as above, effectively to avoid occurring dephasign or unformed phase at reaction interface place, for correlated response provides a series of magnetic that can effectively replace to carry modifying titanium-silicon molecular sieve.
For achieving the above object, the technical scheme of the invention is achieved in that a kind of method using micro passage reaction production Magnetic titanium silicon molecular sieve as above, comprises the steps,
(1), by a certain amount of silicon source, titanium source is made into the mixed solution A of alcohol; A certain amount of modified metal source and template are made into mixing solutions B; Wherein silicon source, titanium source, the mol ratio of modified metal source and template is 1:(0.001 ~ 0.2): (0.006 ~ 0.3): (0.2 ~ 0.8); The solution A prepared and solution B are joined in micro passage reaction, wherein, solution B sends into micro passage reaction through No. two feed duct simultaneously, and in the adherent flowing that faces down of static cutting disk inner chamber, forms liquid film through falling liquid film microchannel; Solution A sends into spraying gun through a feed duct, the liquid band of annular distribution is formed through spraying gun, liquid band with flow through the liquid film pre-mixing that falling liquid film microchannel formed, bottom reducing along static cutting disk inner chamber continues flowing, fluid instantaneous mixing in atwirl microchannel also generates little crystal seed fast, and the mother solution C of formation sends micro passage reaction by the discharging supply pipe bottom movable grinding disc;
(2), SiO will be had
2the Fe that shell is coated
3o
4/ SiO
2magnetic particle evenly spreads in mother solution C, wherein Fe
3o
4/ SiO
2the mass concentration of particle is 0.2 ~ 20kg/m
3, normal temperature, after aging 1 ~ 3 hour, is transferred to closed reactor, and under 160 ~ 200 DEG C of autogenous pressure conditions, absorption regeneration is long 24 ~ 360 hours, is finally carried out by product washing, dries, roasting, obtains the HTS finished product that magnetic carries modification.
Preferably, in step (2), there is SiO
2the Fe that shell is coated
3o
4/ SiO
2the preparation method of magnetic particle is, by Fe
3o
4magnetic nano-particle, evenly spreads in the organic solvent containing ammoniacal liquor, stirs and adds silicon source, wherein Fe
3o
4the mass concentration of particle is 0.25 ~ 25kg/m
3, the volumetric molar concentration in silicon source is 10
-4~ 0.1mol/L, the volumetric molar concentration of ammonia is 0.01 ~ 5mol/L; After abundant reaction and roasting, obtain that there is SiO
2the Fe that shell is coated
3o
4/ SiO
2magnetic particle.
Preferably, described silicon source is positive silicon ester, water glass, the one in silicon sol; Described titanium source is one or both in positive tetraethyl titanate, tetrabutyl titanate, titanium isopropylate, titanous chloride, titanium tetrachloride.
Preferably, described template is morpholine, methylamine, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, Isopropylamine, isobutylamine, ammoniacal liquor, tetra-alkyl ammonium hydroxide, tetraalkyl brometo de amonio, one or both in tetra-alkyl ammonium chloride.
Preferably, described modified metal source is soluble metallic salt or complex compound, is Ag
+, Li
+, Na
+, K
+, Mg
2+, Co
2+, Ni
2+, Mn
2+, Fe
2+, Zn
2+, Cu
2+, Sn
2+, Al
3+, Cr
3+, V
3+in one or both.
Present invention also offers the application of Magnetic titanium silicon molecular sieve in Ammoximation reaction that a kind of basis uses the method for micro passage reaction production Magnetic titanium silicon molecular sieve to prepare as above.
The present invention, by carrying out analytical calculation to the Flow Field Distribution of reactor, devises a kind of novel micro passage reaction, has secondary Micro Channel Architecture.The static cutting disk inner chamber of reactor has secondary reducing, and direction is contrary, and static cutting disk inner chamber top reducing and falling liquid film drum outer wall form the falling liquid film microchannel of the first step, and static cutting disk inner chamber bottom reducing and movable grinding disc outer side surface form the microchannel of the second stage.The two kinds of solution making to enter reactor occur instantaneously to force microcosmic mixing in reactor, generate little crystal seed at a high speed, and on magnetic nano-particle, then carry out absorption regeneration long, finally obtains magnetic and carry modifying titanium-silicon molecular sieve, significantly improve catalyst performance.
Relative to prior art, the method for micro passage reaction of the present invention and use micro passage reaction production Magnetic titanium silicon molecular sieve, has following advantage:
Two strands of materials that micro passage reaction provided by the invention makes to enter reactor in falling liquid film microchannel and microchannel respectively by drop-liquid film and liquid film-liquid film two kinds of mode Rapid contact, mix within the extremely short time and react, reinforcing mass transfer, improve the little crystal seed generating rate of reaction system, effectively avoid occurring dephasign or unformed phase at reaction interface place.This reactor has falling liquid film microchannel and microchannel two-layer configuration, first form a liquid film in falling liquid film microchannel by action of gravity, adherent falling liquid film, and carry out premix with the liquid band sprayed, then form secondary liquid film, adherent surface helix formula falling liquid film in microchannel by eddy flow and shearing action, simultaneous reactions thing is at liquid film high speed rotary collision, liquid-liquid external phase the contact of stirring than tradition has increased substantially mixed effect, and space scale is micron order, and time scale is Millisecond.This micro passage reaction is being prepared in molecular sieve process, two fluids mixes fully instantaneously, and the batch little crystal seed of generation at a high speed, through subsequent regrowth, obtain magnetic and carry modifying titanium-silicon molecular sieve, this is that the new and effective HTS of preparation provides a kind of novel process.
Compared with existing catalyzer, magnetic of the present invention carries modifying titanium-silicon molecular sieve and has more economic serviceability at industrial circle, and advantage is as follows:
(1) magnetic of the present invention carries modifying titanium-silicon molecular sieve and has better catalytic activity to Ammoximation reaction, is better than general heterogeneous catalyst.
(2) magnetic of the present invention carries modifying titanium-silicon molecular sieve and has magnetic, overcomes little, the difficult shortcoming be separated of Ti-Si nano molecular sieve particle diameter.
(3) magnetic of the present invention carries modifying titanium-silicon molecular sieve, can reuse, and only needs simple roasting can recover the activity of catalyzer.
Accompanying drawing explanation
The accompanying drawing forming a part of the present invention is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form the improper restriction of making the present invention.In the accompanying drawings:
Fig. 1 is the structural representation of the micro passage reaction described in the embodiment of the present invention;
Fig. 2 carries the technical process schematic diagram of modifying titanium-silicon molecular sieve for the production magnetic described in the embodiment of the present invention;
Fig. 3 is the Fe in embodiment 1
3o
4the SEM figure of magnetic particle;
Fig. 4 is SiO
2fe after coated
3o
4/ SiO
2the SEM figure of particle;
Fig. 5 is the SEM figure that magnetic carries modifying titanium-silicon molecular sieve finished product;
Fig. 6 is that the magnetic in embodiment 1 carries the magnetic hysteresis loop of modifying titanium-silicon molecular sieve and the Magneto separate design sketch of post catalyst reaction.
In Fig. 1,1, shell of reactor; 2, capping; 3, main regulation dish; 4, a feed duct; 5, No. two feed duct; 6, static cutting disk; 7, movable grinding disc; 8, discharging propeller runner; 9, spraying gun; 10, discharging supply pipe; 11, cooling channel; 12, falling liquid film cylinder; 13, tapping channel; 14, reactor base; 15, turning axle; 16, motor; 17, sealing member; 18, auxiliary adjustment disk.
Embodiment
It should be noted that, when not conflicting, the embodiment in the present invention and the feature in embodiment can combine mutually.Simultaneously convenient in order to describe, the device in the present invention omits the traditional valve on pipeline, and the mouth of pipe conventional on reactor, manhole, the annexes such as instrumentation tap, the technician of the industry can design as required.The technician of the industry can make more multiple changing type and improvement, such as, change charging metering method, adjust the mouth of pipe specification of micro passage reaction, and increase interface quantity, all these modification, adjustment, improvement all should be considered as protection scope of the present invention.
In the embodiment of the present invention, agents useful for same all adopts analytical reagent, and water used is deionized water, prepares magnetic and carries the technical process of modifying titanium-silicon molecular sieve as shown in Figure 2.SEM adopts Japanese HitachiS-4700 type sem test; Magnetic hysteresis loop adopts LDJ 9600 to shake sample magnetometer test.
Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
A kind of micro passage reaction, comprise capping 2, shell of reactor 1, reactor base 14, main regulation dish 3 and auxiliary adjustment disk 18, described shell of reactor 1 is fixed on reactor base 14, motor 16 is provided with in described shell of reactor 1, described motor 16 is connected with turning axle 15, and described turning axle 15 is provided with movable grinding disc 7, and movable grinding disc 7 outer race is equipped with static cutting disk 6, static cutting disk 6 is arranged on the inwall of shell of reactor 1, and capping 2 is arranged on above static cutting disk 6; Described capping 2 is provided with a feed duct 4 and falling liquid film cylinder 12, and feed duct 4 is positioned at the inside of falling liquid film cylinder 12, is provided with spraying gun 9 bottom a described feed duct 4; Described capping 2 is provided with No. two feed duct 5, and described No. two feed duct 5 are between falling liquid film cylinder 12 and static cutting disk 6; Be provided with tapping channel 13 between described movable grinding disc 7 and reactor base 14, and described shell of reactor 1 is provided with discharging supply pipe 10, described tapping channel 13 is corresponding with the position of discharging supply pipe 10; Be provided with cooling channel 11 in described static cutting disk 6, described cooling channel 11 be connected with import and the outlet of circulating cooling medium; Described turning axle 15 is provided with sealing member 17 through the position of tapping channel 13; Be provided with discharging propeller runner 8 bottom described movable grinding disc 7, be fixed on turning axle 15.
Described main regulation dish 3 is arranged between shell of reactor 1 and capping 2; Described auxiliary adjustment disk 18 is arranged on capping 2 top, and corresponding with the position of falling liquid film cylinder 12.
Described static cutting disk 6 inner chamber has secondary reducing, and from top to bottom, diameter successively decreases upper part of described static cutting disk 6 gradually, is top reducing; From top to bottom, diameter increases progressively lower part of static cutting disk 6 gradually, is bottom reducing; And the top reducing of described static cutting disk 6 inner chamber and falling liquid film cylinder 12 outer wall form the falling liquid film microchannel of the first step, static cutting disk 6 inner chamber bottom reducing and movable grinding disc 7 outer side surface form the microchannel of the second stage; Movable grinding disc 7 is up-thin-low-thick " loudspeaker " type structure, corresponding with the bottom reducing wall configuration of static cutting disk 6;
Embodiment 1
Described static cutting disk 6 inner chamber has secondary reducing, and from top to bottom, diameter successively decreases upper part of described static cutting disk 6 gradually, is top reducing; From top to bottom, diameter increases progressively lower part of static cutting disk 6 gradually, is bottom reducing; And the top reducing of described static cutting disk 6 inner chamber and falling liquid film cylinder 12 outer wall form the falling liquid film microchannel of the first step, the outlet of falling liquid film microchannel is of a size of 400 microns, static cutting disk 6 inner chamber bottom reducing and movable grinding disc 7 outer side surface form the microchannel of the second stage, and the thickness of microchannel is of a size of 700 microns; Movable grinding disc 7 is up-thin-low-thick " loudspeaker " type structure, corresponding with the bottom reducing wall configuration of static cutting disk 6; The tapering of the top reducing of described static cutting disk 6 inner chamber is 15 °; The radian of described movable grinding disc 7 longitudinal axes tangent plane upper side edge is 40 °.
The wall of static cutting disk 6 inner chamber bottom reducing and movable grinding disc 7 outer side surface all have radial arrangement, the teeth groove that dislocation is corresponding, groove depth 500um, groove width 800um;
Above-mentioned micro passage reaction is carried HTS for the preparation of the magnetic of silver-colored modification, and its concrete steps are:
(1) by tetraethoxy, positive tetraethyl titanate and Virahol are made into mixed solution A, and Silver Nitrate and morpholine are made into mixing solutions B; Wherein tetraethoxy, positive tetraethyl titanate, the mol ratio of Silver Nitrate and morpholine is 1:0.025:0.03:0.4, [SiO
2]=1.0mol/L; The solution A prepared and solution B are joined in micro passage reaction, wherein, solution A flows through a feed duct 4 simultaneously, sends into spraying gun 9, forms the liquid band of annular distribution through spraying gun 9; Solution B flows through No. two feed duct 5, in the adherent flowing that faces down of static cutting disk 6 inner chamber, forms liquid film through falling liquid film microchannel; Liquid band with flow through the liquid film pre-mixing that falling liquid film microchannel formed, flowing is continued along bottom reducing, instantaneous mixing in atwirl microchannel also generates little crystal seed fast, the mother solution C formed sends reactor by the discharging supply pipe 10 bottom mill, wherein, the rotating speed of movable grinding disc 7 is 3000 revs/min, and discharging supply pipe 10 mixed solution flow is 500kg/h.
(2) Fe prepared by solvent-thermal method
3o
4magnetic nano-particle, evenly spreads in the ethanol/water mixed solvent containing ammoniacal liquor, stirs and adds tetraethoxy, fully reacts and after roasting, obtains having SiO
2the Fe that shell is coated
3o
4/ SiO
2magnetic particle; Wherein Fe
3o
4the mass concentration of particle is 1.0kg/m
3, the volume ratio of ethanol/water mixed solvent is 4:1, and the volumetric molar concentration in silicon source is 1.5x10
-3mol/L, the volumetric molar concentration of ammonia is 0.15mol/L;
(3) Fe will obtained
3o
4/ SiO
2magnetic nano-particle evenly spreads in mother solution C, wherein Fe
3o
4/ SiO
2the mass concentration of particle is 1.0kg/m
3normal temperature is after aging 1 hour, be transferred to closed reactor, regrowth 48 hours under 200 DEG C of autogenous pressure conditions, finally product carried out washing, 100 DEG C of dryings 6 hours, be warmed up to 550 DEG C of roastings 5 hours with 1 DEG C/min rate program, removing template, the magnetic obtaining silver-colored modification carries HTS finished product.
The magnetic utilizing above-mentioned technique to prepare silver-colored modification carries HTS, and the appearance structure of each intermediate and final finished, as shown in Fig. 3 ~ Fig. 5, is respectively Fe
3o
4magnetic particle, SiO
2coated Fe
3o
4/ SiO
2the magnetic of particle and silver-colored modification carries the SEM figure of HTS finished product.
Embodiment 2
Described static cutting disk 6 inner chamber has secondary reducing, and from top to bottom, diameter successively decreases upper part of described static cutting disk 6 gradually, is top reducing; From top to bottom, diameter increases progressively lower part of static cutting disk 6 gradually, is bottom reducing; And the top reducing of described static cutting disk 6 inner chamber and falling liquid film cylinder 12 outer wall form the falling liquid film microchannel of the first step, the outlet of falling liquid film microchannel is of a size of 500 microns, static cutting disk 6 inner chamber bottom reducing and movable grinding disc 7 outer side surface form the microchannel of the second stage, and microchannel thickness is of a size of 600 microns; Movable grinding disc 7 is up-thin-low-thick " loudspeaker " type structure, corresponding with the bottom reducing wall configuration of static cutting disk 6; The tapering of the top reducing of described static cutting disk 6 inner chamber is 30 °; The radian of described movable grinding disc 7 longitudinal axes tangent plane upper side edge is 60 °.
Wall and movable grinding disc 7 outer side surface of static cutting disk 6 inner chamber bottom reducing all have helical arrangement, the teeth groove that dislocation is corresponding, groove depth 300um, groove width 900um;
Above-mentioned micro passage reaction is carried HTS for the preparation of cobalt improved magnetic, and its concrete steps are:
(1) tetraethoxy and ethylene glycol are made into mixed solution A, by titanous chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and tetraethylammonium bromide are made into mixing solutions B; Wherein tetraethoxy, titanous chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and tetraethylammonium bromide mol ratio are 1:0.05:0.07:0.3, [SiO
2]=2.5mol/L; The solution A prepared and solution B are joined in micro passage reaction, wherein, solution A flows through a feed duct 4 simultaneously, sends into spraying gun 9, forms the liquid band of annular distribution through spraying gun 9; Solution B flows through No. two feed duct 5, in the adherent flowing that faces down of static cutting disk 6 inner chamber, forms liquid film through falling liquid film microchannel; Liquid band with flow through the liquid film pre-mixing that falling liquid film microchannel formed, flowing is continued along bottom reducing, instantaneous mixing in atwirl microchannel also generates little crystal seed fast, the mother solution C formed sends reactor by the discharging supply pipe 10 bottom mill, wherein, the rotating speed of movable grinding disc 7 is 5000 revs/min, and discharging supply pipe 10 mixed solution flow is 600kg/h.
(2) Fe prepared by solvent-thermal method
3o
4magnetic nano-particle, evenly spreads in the ethanol/water mixed solvent containing ammoniacal liquor, stirs and adds tetraethoxy, fully reacts and after roasting, obtains having SiO
2the Fe that shell is coated
3o
4/ SiO
2magnetic particle; Wherein Fe
3o
4the mass concentration of particle is 4.0kg/m
3, the volume ratio of ethanol/water mixed solvent is 1:1, and the volumetric molar concentration in silicon source is 5.5x10
-3mol/L, the volumetric molar concentration of ammonia is 0.5mol/L;
(3) Fe will obtained
3o
4/ SiO
2magnetic nano-particle evenly spreads in mother solution C, wherein Fe
3o
4/ SiO
2the mass concentration of particle is 2.0kg/m
3normal temperature is after aging 2 hours, be transferred to closed reactor, regrowth 96 hours under 160 DEG C of autogenous pressure conditions, finally product carried out washing, 90 DEG C of dryings 5 hours, be warmed up to 750 DEG C of roastings 10 hours with 0.5 DEG C/min rate program, removing template, obtains cobalt improved magnetic and carries HTS finished product.
Embodiment 3
The magnetic adopting the micro passage reaction of embodiment 1 to prepare aluminium modification carries HTS, and its concrete steps are:
By tetraethoxy, positive metatitanic acid orthocarbonate and ethanol are made into mixed solution A, and aluminum nitrate and 4-propyl bromide are made into mixing solutions B; Wherein tetraethoxy, positive metatitanic acid orthocarbonate, aluminum nitrate and 4-propyl bromide mol ratio are 1:0.04:0.04:0.5, [SiO
2]=1.5mol/L; The solution A prepared and solution B are joined in micro passage reaction simultaneously, wherein, solution A flows through a feed duct 4, solution B flows through No. two feed duct 5, instantaneous mixing in atwirl microchannel also generates little crystal seed fast, the mother solution C formed sends reactor by the discharging supply pipe 10 bottom mill, wherein, falling liquid film microchannel size is regulated to be 700 microns, microchannel size is 900 microns, the rotating speed of movable grinding disc is 7000 revs/min, and discharging supply pipe mixed solution flow is 900kg/h.
Fe prepared by solvent-thermal method
3o
4magnetic nano-particle, evenly spreads in the ethanol/water mixed solvent containing ammoniacal liquor, stirs and adds tetraethoxy, fully reacts and after roasting, obtains having SiO
2the Fe that shell is coated
3o
4/ SiO
2magnetic particle; Wherein Fe
3o
4the mass concentration of particle is 8.0kg/m
3, the volume ratio of ethanol/water mixed solvent is 1:4, and the volumetric molar concentration in silicon source is 11.2x10
-3mol/L, the volumetric molar concentration of ammonia is 1.3mol/L;
By the Fe obtained
3o
4/ SiO
2magnetic nano-particle evenly spreads in mother solution C, wherein Fe
3o
4/ SiO
2the mass concentration of particle is 5.0kg/m
3normal temperature is after aging 3 hours, be transferred to closed reactor, regrowth 120 hours under 180 DEG C of autogenous pressure conditions, finally product carried out washing, 100 DEG C of dryings 10 hours, be warmed up to 600 DEG C of roastings 8 hours with 0.5 DEG C/min rate program, removing template, the magnetic obtaining aluminium modification carries HTS finished product.
Carry HTS for blank sample with unmodified magnetic, respectively the magnetic of modification in embodiment 1 ~ embodiment 3 is carried the Ammoximation reaction that HTS is used for pimelinketone.Reaction conditions is 80 DEG C of oil baths, reaction is carried out in confined reaction bottle, add the 50ml trimethyl carbinol, 8g pimelinketone, 15g25% ammoniacal liquor, 2g modification magnetic carry HTS, 10g hydrogen peroxide micro-sampling pump slowly adds, by the transformation efficiency of product Shimadzu GC-2014 gas chromatographic detection pimelinketone that obtains and the selectivity of cyclohexanone-oxime after reaction 1h, concrete outcome is in table 1; Wherein, the Magneto separate effect of catalyst recovery is carried out after the magnetic hysteresis loop of the finished product molecular sieve obtained in embodiment 1 and reaction, as shown in Figure 6.
Wherein, the transformation efficiency of pimelinketone and the selectivity of cyclohexanone-oxime calculate as follows:
Pimelinketone amount/reactant pimelinketone amount × 100% of pimelinketone transformation efficiency (%)=conversion
Amount × 100% of the pimelinketone of pimelinketone amount/conversion that cyclohexanone-oxime selectivity (%)=generation cyclohexanone-oxime consumes
Concrete analysis the results are shown in following table.
Table 1
| Catalyzer | Transformation efficiency | Selectivity |
| Blank sample | 82.1％ | 90.6％ |
| Embodiment 1 | 95.8％ | 97.5％ |
| Embodiment 2 | 97.3％ | 99.4％ |
| Embodiment 3 | 96.7％ | 98.2％ |
Known by contrast reaction result, use micro passage reaction of the present invention to prepare magnetic and carry modifying titanium-silicon molecular sieve, for the Ammoximation reaction of pimelinketone, carry HTS than there is no the magnetic of modification and there is higher selectivity and activity.
The foregoing is only the preferred embodiment of the invention; not in order to limit the invention; within all spirit in the invention and principle, any amendment done, equivalent replacement, improvement etc., within the protection domain that all should be included in the invention.
Claims (10)
1. a micro passage reaction, comprise capping (2), shell of reactor (1) and reactor base (14), described shell of reactor (1) is fixed on reactor base (14), it is characterized in that: in described shell of reactor (1), be provided with motor (16), described motor (16) is connected with turning axle (15), and described turning axle (15) is provided with movable grinding disc (7), movable grinding disc (7) outer race is equipped with static cutting disk (6), static cutting disk (6) is arranged on the inwall of shell of reactor (1), capping (2) is arranged on static cutting disk (6) top, described capping (2) is provided with a feed duct (4) and falling liquid film cylinder (12), and feed duct (14) is positioned at the inside of falling liquid film cylinder (12), a described feed duct (4) bottom is provided with spraying gun (9), described capping (2) is provided with No. two feed duct (5), and described No. two feed duct (5) are positioned between falling liquid film cylinder (12) and static cutting disk (6), tapping channel (13) is provided with between described movable grinding disc (7) and reactor base (14), and described shell of reactor (1) is provided with discharging supply pipe (10), described tapping channel (13) is corresponding with the position of discharging supply pipe (10), preferably, in described static cutting disk (6), be provided with cooling channel (11), described cooling channel (11) be connected with import and the outlet of circulating cooling medium, preferably, described turning axle (15) is provided with sealing member (17) through the position of tapping channel (13), preferably, described movable grinding disc (7) bottom is provided with discharging propeller runner (8), is fixed on movable grinding disc (7) or turning axle (15).
2. micro passage reaction according to claim 1, is characterized in that: described static cutting disk (6) inner chamber has secondary reducing, and from top to bottom, diameter successively decreases upper part of described static cutting disk (6) gradually, is top reducing; From top to bottom, diameter increases progressively lower part of static cutting disk (6) gradually, is bottom reducing; And the top reducing of described static cutting disk (6) inner chamber and falling liquid film cylinder (12) outer wall form the falling liquid film microchannel of the first step, static cutting disk (6) inner chamber bottom reducing and movable grinding disc (7) outer side surface form the microchannel of the second stage; Movable grinding disc (7) is up-thin-low-thick " loudspeaker " type structure, corresponding with the bottom reducing wall configuration of static cutting disk (6); Preferably, the tapering of the top reducing of described static cutting disk (6) inner chamber is 3 ~ 60 °; The radian of the outer wall circular arc of described movable grinding disc (7) is 10 ~ 80 °.
3. micro passage reaction according to claim 1 and 2, it is characterized in that: also comprise main regulation dish (3) and auxiliary adjustment disk (18), described main regulation dish (3) is arranged between shell of reactor (1) and capping (2); Described auxiliary adjustment disk (18) is arranged on capping (2) top, and corresponding with the position of falling liquid film cylinder (12).
4. micro passage reaction according to claim 1 and 2, it is characterized in that: the teeth groove that the wall of described static cutting disk (6) inner chamber bottom reducing all has arrangement mode different from movable grinding disc (7) outer side surface, preferably, teeth groove is twill, radial direction or spirrillum.
5. use a method for the micro passage reaction production Magnetic titanium silicon molecular sieve as described in any one of Claims 1 to 4, it is characterized in that: comprise the steps:
(1), by a certain amount of silicon source, titanium source is made into the mixed solution A of alcohol; A certain amount of modified metal source and template are made into mixing solutions B; Wherein silicon source, titanium source, the mol ratio of modified metal source and template is 1:(0.001 ~ 0.2): (0.006 ~ 0.3): (0.2 ~ 0.8); The solution A prepared and solution B are joined in micro passage reaction simultaneously, wherein, solution B sends into micro passage reaction through No. two feed duct (5), and in the adherent flowing that faces down of static cutting disk (6) inner chamber, forms liquid film through falling liquid film microchannel; Solution A sends into spraying gun (9) through a feed duct (4), the liquid band of annular distribution is formed through spraying gun (9), liquid band with flow through the liquid film pre-mixing that falling liquid film microchannel formed, bottom reducing along static cutting disk (6) inner chamber continues flowing, fluid instantaneous mixing in atwirl microchannel also generates little crystal seed fast, and the mother solution C of formation sends micro passage reaction by the discharging supply pipe (10) of movable grinding disc (7) bottom;
(2), SiO will be had
2the Fe that shell is coated
3o
4/ SiO
2magnetic particle evenly spreads in mother solution C, wherein Fe
3o
4/ SiO
2the mass concentration of particle is 0.2 ~ 20kg/m
3, normal temperature, after aging 1 ~ 3 hour, is transferred to closed reactor, and under 160 ~ 200 DEG C of autogenous pressure conditions, absorption regeneration is long 24 ~ 360 hours, is finally carried out by product washing, dries, roasting, obtains the HTS finished product that magnetic carries modification.
6. the method for use micro passage reaction production Magnetic titanium silicon molecular sieve according to claim 5, is characterized in that: step has SiO in (2)
2the Fe that shell is coated
3o
4/ SiO
2the preparation method of magnetic particle is, by Fe
3o
4magnetic nano-particle, evenly spreads in the organic solvent containing ammoniacal liquor, stirs and adds silicon source, wherein Fe
3o
4the mass concentration of particle is 0.25 ~ 25kg/m
3, the volumetric molar concentration in silicon source is 10
-4~ 0.1mol/L, the volumetric molar concentration of ammonia is 0.01 ~ 5mol/L; After abundant reaction and roasting, obtain that there is SiO
2the Fe that shell is coated
3o
4/ SiO
2magnetic particle.
7. the method for the use micro passage reaction production Magnetic titanium silicon molecular sieve according to claim 5 or 6, is characterized in that: described silicon source is positive silicon ester, water glass, the one in silicon sol; Described titanium source is one or both in positive tetraethyl titanate, tetrabutyl titanate, titanium isopropylate, titanous chloride, titanium tetrachloride.
8. the method for the use micro passage reaction production Magnetic titanium silicon molecular sieve according to claim 5 or 6, it is characterized in that: described template is morpholine, methylamine, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, Isopropylamine, isobutylamine, ammoniacal liquor, tetra-alkyl ammonium hydroxide, tetraalkyl brometo de amonio, one or both in tetra-alkyl ammonium chloride.
9. the method for the use micro passage reaction production Magnetic titanium silicon molecular sieve according to claim 5 or 6, it is characterized in that: described modified metal source is soluble metallic salt or complex compound, is Ag
+, Li
+, Na
+, K
+, Mg
2+, Co
2+, Ni
2+, Mn
2+, Fe
2+, Zn
2+, Cu
2+, Sn
2+, Al
3+, Cr
3+, V
3+in one or both.
10. the method for the use micro passage reaction production Magnetic titanium silicon molecular sieve according to any one of claim 5 ~ 9, the Magnetic titanium silicon molecular sieve of preparation is applied in Ammoximation reaction.
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| CN114798076A (en) * | 2022-04-02 | 2022-07-29 | 深圳市锦昊辉实业发展有限公司 | Grinding equipment is used in transparent powder production |
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