CN108191794A - A kind of propylene ring oxidation reaction method - Google Patents
A kind of propylene ring oxidation reaction method Download PDFInfo
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- CN108191794A CN108191794A CN201711469399.8A CN201711469399A CN108191794A CN 108191794 A CN108191794 A CN 108191794A CN 201711469399 A CN201711469399 A CN 201711469399A CN 108191794 A CN108191794 A CN 108191794A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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Abstract
The invention discloses a kind of epoxidation of propylene methods, are in magnetically stabilized bed reactor, by propylene and solvent, H2O2Mixture and have magnetic Ti MWW molecular sieve catalyst haptoreactions, be 25~100 DEG C in temperature, pressure is 0.1~10.0MPa, and propylene weight air speed is 0.1~15h‑1, magnetic field intensity be 100~1000 oersteds under conditions of reacted, propylene is made to be converted into propylene oxide.The yield and selectivity of the product propene oxide of the reaction are respectively greater than 92% and more than 98%, H2O2Conversion ratio and utilization rate are respectively greater than 98% and more than 93%, and product quality improves, and reaction efficiency also improves, and reduces separating-purifying cost.Compared with fluidized-bed process method, due to magnetic field bubble crushing, thus mass-transfer efficiency is high, catalyst is taken out of less, advantageously reduces energy consumption, reduces environmental pollution, and improves device working ability.
Description
Technical field
The invention belongs to the preparation methods of known compound, and in particular to one kind in magnetic stablizing bed middle composite magnetic Ti-
The method that MWW molecular sieve catalytic propylene ring oxidation reactions prepare propylene oxide.
Background technology
Propylene oxide (PO) is a kind of important large industrial chemicals, because it is with the very big oxygen-containing three-membered ring of tension, is changed
It is very active to learn property, it is widely used, mainly for the production of polyethers, further produce polyurethane plastics, foam stabiliser, papermaking
Industrial defoaming agent, crude oil demulsifier, oil well acid processing wetting agent and high-effective low foam detergent etc..Propylene oxide is also used for producing third
Glycol, and then produce unsaturated polyester resin etc..With the expansion of propylene oxide purposes and the continuous growth of downstream product dosage,
The particularly prosperity of the industries such as automobile, building household, increases considerably polyurethane and nonionic surfactant demand,
The market demand for leading to propylene oxide is vigorous.
At present, in the world the industrial process of propylene oxide mainly have chlorohydrination method, conjugated oxidation (also referred to as co-production method,
Indirect oxidation method), production phenols (CHP methods) and H2O2Direct oxidation method (HPPO methods), wherein HPPO methods are because environmentally friendly without dirt
It contaminates and becomes the emphasis researched and developed now, and tend to be ripe, show good industrial prospect.With TS-1 and Ti-MWW points
Son sieve may be used as new process (HPPO) catalyst of propylene propylene oxide.HPPO process optimum solvents are respectively methanol and second
Nitrile, principal product are propylene oxide.
N series connection fixed bed reactors are disclosed in patent CN103724299B as propylene ring oxidation reaction, raw material is pressed
It sequentially enters in series connection fixed bed reactors according to logistics direction, is connect with the catalyst of TS-1 type Titanium Sieve Molecular Sieve in each reactor
It touches, generation includes the product of propylene oxide.According to material flow direction series arrangement each reactor reaction temperature successively
Successively decrease.What the n section that patent CN101941954B describes the integer that a kind of catalyst bed is divided into more than 2 was used in series
Fixed bed reactors, for H2O2Propylene oxide is prepared with propylene.
Patent CN104130216B develops a kind of H2O2Direct oxidation propylene/propane gaseous mixture is anti-using fluid bed circulation
The technique for answering device continuous preparation of epoxypropane.Slurry withdrawal respectively mixes hypoxemia propylene/propane by flash column in the technique
Gas and propylene oxide steam, and the mother liquor containing catalyst carries out separate fine particles molecular sieve catalyst slurries and mother through membrane separator
Liquid, mother liquor is after flash separation methanol, after synchronizing recycling reaction in hyperoxia propylene/propane absorption tower using recycling design methanol
The hyperoxia propylene/propane gaseous mixture of remnants simultaneously recycles, and catalyst slurry Returning reactor cycle after line partial regeneration makes
With.
Patent CN101456849B develops a kind of carbon dioxide and is catalyzed propylene ring at supercritical conditions for reaction medium
Oxidation prepares the method and device of propylene oxide.First add in big grain size TS-1 catalyst, then add in gas reactant propylene in
In mixer, and liquid reactants H is added in a mixer2O2Aqueous solution and cosolvent methanol, carbon dioxide be passed through mixer
With propylene, H2O2Aqueous solution and cosolvent methanol mixing after enter reactor in react, obtain reaction product propylene oxide.
Invention content
The present invention seeks to be directed in current propylene ring oxidation reaction to use excessively high fixed bed pressure drop, generation channel and part
The problem of crossing heat affecting reactivity worth, also solves the alternate back-mixing of fluid bed and particle leakage causes what catalytic performance declined
Problem developed the combined new process of magnetic stablizing bed and a kind of composite magnetic Ti-MWW molecular sieve catalysts, improve
The activity of propylene conversion and the selectivity of product.
It is used in the present invention it is magnetic stablizing bed be a kind of novel reaction bed form, have fixed bed and many of fluid bed concurrently
Advantage.Compared with fluid bed, externally-applied magnetic field can effectively control alternate back-mixing and particle leakage；Compared with fixed bed, magnetic is steady
Fixed bed can use catalyst particle, and without causing high pressure drop, uniform voidage can make bed that should not generate channel drawn game
Portion overheats.In addition, it is magnetic stablizing bed can also stable operation in a wider scope, and can bubble crushing improve interphase mass transfer.Tool
There is the magnetic stablizing bed of more than characteristic to have good application prospect in propylene ring oxidation reaction.But these advantages are given full play to,
It must make catalyst that there is magnetic response characteristic first, it can the present invention also provides a kind of composite magnetic Ti-MWW molecular sieve catalysts
Match very well with magnetic stablizing bed, form a kind of innovative technology method of combination, there is good application prospect.
The present invention provides a kind of production methods of propylene oxide, it is characterised in that：Magnetic field intensity for 100~1000 it is difficult to understand this
It is special it is magnetic stablizing bed under conditions of temperature is 25~100 DEG C and pressure is 0.5~10.0MPa, by propylene, H2O2Solution has
Solvent and composite magnetic Ti-MWW molecular sieve catalysts haptoreaction generation propylene oxide, propylene weight air speed for 0.1~
15h-1。
Magnetically stabilized bed reactor described above is made of reactor and externally-applied magnetic field, externally-applied magnetic field be along reactor axis to
Uniform steady magnetic field, uniform magnetic field are carried by DC power supply and the helmholtz coil coaxial with reactor or uniform high-density solenoid
For having ferromagnetic catalyst to attract each other and be stable in the presence of in reactor due to the magnetization in the magnetic field.
In the present invention, reaction carries out in the presence of an organic.Available organic solvent includes such as alcohols (first
Alcohol, tert-butyl alcohol etc.), ketone compounds (acetone etc.), ether compound (1,4- dioxanes etc.), ester type compound (methyl acetate,
Ethyl acetate etc.), nitrile compounds (acetonitrile, propionitrile etc.), hydrocarbon (normal heptane, toluene etc.), halogenated hydrocarbons (1,2- dichloroethanes etc.)
Organic compound etc..
Composite magnetic Ti-MWW molecular sieve catalysts described above are Ti-MWW points using inorganic particle material as kernel
Son sieve is shell.
Magnetic stablizing bed middle reaction condition of the present invention is preferably：35~65 DEG C, 0.5~5.0MPa, propylene weight air speed
0.5~8.0h-1, 100~500 oersted of magnetic field intensity.
The organic solvent used in the propylene ring oxidation reaction be preferably acetonitrile, acetone, propionitrile, 1,2- dichloroethanes or
Toluene, further preferred acetonitrile.
Reaction process of the present invention is characterized in that：Total weight based on liquid feed stream, ethane nitrile content for 60~
75wt%, H2O2Content is 7~28wt%；Propylene and H2O2Molar ratio be 2.0~5.0；
Magnetic coupling catalyst material of the present invention, the inorganic particle material of kernel is Fe3O4、γ-Fe2O3、
NiFe2O4、CuFe2O4One or more of.
Composite magnetic Ti-MWW molecular sieve catalyst preparation method characteristics of the present invention are：By inorganic particle material
Material is mixed into 25~50wt% slurries spray drying formings with Ludox, pore-foaming agent, deionized water and obtains 30~100 microns of microballoons
Particle；Titanium source solution according to H2O2Solution quality ratio is 1:(2~10) are added drop-wise to a concentration of 25~50% H2O2In solution,
And it is stirred to obtain Ti solution, then boron source is added to be stirred to obtain mixed liquor simultaneously；Then by obtained magnetic microsphere and organic
Amine template (OSDA) agent adds in above-mentioned mixed liquor, is uniformly mixed, obtaining a mole composition in mix slurry is：SiO2：
(0.017~0.033) TiO2：(0.2~1.5) B2O3：(0.05~5.0) OSDA：(20~150) H2O, at 150~200 DEG C
Crystallization 2~14 days, filtered, washing, dry and 450~650 DEG C of roastings obtain composite magnetic Ti-MWW molecular screen primary powders, then will
Original powder is removed in the outer Ti of skeleton and skeleton after B element with mineral acid treatment, then is answered within 3~20 hours through 500~700 DEG C of roastings
Close magnetism Ti-MWW molecular sieve catalysts.
Pore-foaming agent used in building-up process of the present invention includes：Sesbania powder, methylcellulose, polymethacrylates,
Appoint in polyvinylpyrrolidone, PolyTHF, polyisobutene, polyethylene oxide, polystyrene, polyamide, polyacrylate
It is a kind of.
Titanium source described in building-up process of the present invention is tetralkyl titanate, halogenated titanium or titanium oxide, and the silicon source is
Silica, Ludox or ethyl orthosilicate, the boron source are boric acid or borate, and the organic amine template is piperidines
Or hexamethylene imine.
Composite Ti-MWW molecular screen primary powders described in building-up process of the present invention and a concentration of 0.1~5.0mol/L acid solutions
It is 1 according to weight ratio：(5~100) prepare reaction mixture, and the acid is inorganic acid or organic acid, and inorganic acid is hydrochloric acid, sulphur
Acid, nitric acid or phosphoric acid, organic acid are formic acid, acetic acid, propionic acid, citric acid or tartaric acid, and it is small to handle 0.5~72 in 50~200 DEG C
When, filtered, washing, drying obtain acid-treated product.
The composite magnetic Ti-MWW molecular sieve catalyst preparation method characteristics are：By inorganic particle material and silicon
Colloidal sol, pore-foaming agent, deionized water are mixed into 25~50wt% slurries spray drying formings and obtain 30~100 microns of microsphere particles；
Then crystallization is mixed with titanium source, boron source and template and obtains composite magnetic Ti-MWW molecular screen primary powders, it will be after drying and roasting
The outer Ti of original powder and mineral acid treatment removing skeleton and skeleton in after B element, obtain composite magnetic Ti-MWW molecular sieve catalysts.
Pore-foaming agent used in preparation method of the present invention includes：Sesbania powder, methylcellulose, polymethylacrylic acid
In ester, polyvinylpyrrolidone, PolyTHF, polyisobutene, polyethylene oxide, polystyrene, polyamide, polyacrylate
It is any.
Magnetically stabilized bed reactor provided by the invention is that there are uniform magnetic fields in the reactor, has ferromagnetic adsorbent
It is attracted each other and is stable in the presence of in reactor not with the reactor of Flow of Goods and Materials due to the magnetization in the magnetic field, it is by anti-
Device and externally-applied magnetic field is answered to form, externally-applied magnetic field be along reactor axis to uniform steady magnetic field, uniform magnetic field by DC power supply and
A series of helmholtz coils coaxial with reactor or uniform high-density solenoid provide, reactor and the other components of reactor by
The good material of magnetic permeability is made.
The online handling method of catalyst is in the present invention：Fine grained fresh catalyst is molten with reaction in catalyst preparation kettle
Agent is configured to slurries, and magnetic stablizing bed top is then squeezed into catalyst charge pump, and due to the effect in magnetic field, catalyst residence exists
In magnetically stabilized bed reactor；The decaying catalyst of magnetically stabilized bed reactor bottom and the slurries of material are accomplished continuously or intermittently steady from magnetic
The catalyst of fixed bed bottom unloads outlet discharge magnetically stabilized bed reactor, carries out separation of solid and liquid, separates solid dead catalyst, liquid follows
Ring uses.
The grain size of catalyst described in method provided by the invention can be 30~100 microns, preferred grain size for 30~
70 microns, catalyst granules can be individually placed in magnetically stabilized bed reactor.The catalyst, which can be fixed, is present in reactor
In, it can also continuously or intermittently pass in and out reactor according to the needs of operation.
Method provided by the invention, due to the use of magnetically stabilized bed reactor and composite magnetic Ti-MWW molecular sieve catalysts,
Compared with existing fluid bed or fixed bed HPPO techniques, advantage is：
(1) compared with existing fixed bed reactors process, with bed pressure drop is low, mass-transfer efficiency is high, side reaction
The advantages of few；Compared with ordinary fluidized bed reactor process method, due to magnetic field bubble crushing, thus mass-transfer efficiency is high, catalysis
Agent is taken out of few.Catalyst consumption is low, and catalyst is not required to detach with reaction mass, and flow is simple, easy to operate, and can add outside
Under the action of magnetic field, easily load and unload catalyst and carry out ex-situ regeneration；Also have that opereating specification is wide, reaction stream air speed simultaneously
The advantages that raising, reaction mass transfer, high heat transfer efficiency.
(2) the magnetic coupling molecular sieve catalyst of small particle has been used, has improved reaction efficiency, propylene conversion and product
Selectivity is respectively greater than 92% and 99%, H2O2Conversion ratio and effective rate of utilization be respectively greater than 98% and 93%, product quality carries
Height also saves the expense of subsequent product purification.
Used in magnetically stabilized bed reactor particle it is tiny (<Catalyst 0.15mm) is without increasing bed layer pressure
Drop, with used in paste state bed reactor bulky grain (>0.8mm) catalyst is compared, and the method for the present invention substantially improves gas-solid phase
The effect of mass-and heat-transfer is showed off one's talent or competence consumption so as to reduce dress.
Since used catalyst particle is tiny, thus catalyst pair can be loaded and unloaded at any time during the method for the present invention is implemented
It carries out operating of the ex-situ regeneration without terminating whole device.
Description of the drawings
The invention will be further described with reference to the accompanying drawings and embodiments：
Fig. 1：Magnetic stablizing bed process flow diagram；
In figure, 1, raw material pump, 2, preheater, 3, magnetic stablizing bed, 4, magnetic coil, 5, cooler, 6, separator, 7, magnetic force
Intensity controller.
Specific embodiment
Embodiment and generated effect are further illustrated the present invention by embodiment and comparative example, but the present invention
Protection domain is not limited to the content listed by embodiment.
H is calculated by following calculating formula respectively2O2Conversion ratio, PO (propylene oxide) selectivity, H2O2Effective rate of utilization,
C3H6(propylene) conversion ratio and PO yields.
H2O2Conversion ratio：
PO selectivity：
H2O2Effective rate of utilization：
C3H6Conversion ratio：
PO yields：
C in formula0 H2O2And Ci H2O2The mass concentration of hydrogen peroxide, n before and after Wei not reacting0 C3H6And ni C3H6Third before and after Wei not reacting
The molal quantity of alkene, n0 H2O2And ni H2O2Oxydol H before and after Wei not reacting2O2Molal quantity, npo, nNMEAnd nPGRing after respectively reacting
The amount of the substance of Ethylene Oxide, propylene glycol monomethyl ether and propylene glycol generation.As the index of evaluation response performance, XH2O2, Spo, YpoIt adopts
After reaction 6 hours, every 2 hours test samples, three scale errors of continuous three samples test sample result is made to be less than 2%, simultaneously
Using the average value of these three sample results as reactivity worth index.
Comparative example 1
Ti-MWW molecular sieves are synthesized according to document (J.Phys.Chem.B, 2001,105 (15), 2897-2905) method.
TiO in titanium source in molar ratio2：SiO in silicon source2：B in boron source2O3：F- in Fluorine source：Organic formwork agent：
H2O is 0.033：1：0.67：1：1.4：19 prepare reaction mixture, and the titanium source is butyl titanate, and the silicon source is
Silica gel, the boron source be boric acid, the Fluorine source be HF, the organic formwork agent be piperidines, the reaction mixture
It is filtered, washing, dry in 170 DEG C of hydrothermal crystallizings 7 days, obtain Ti-MWW molecular screen primary powders；By Ti-MWW molecular screen primary powders with
A concentration of 2mol/l salpeter solutions are 1 according to weight ratio：50 prepare reaction mixture, are handled 20 hours at 100 DEG C, pass through
Filter, washing, drying obtain product after acid processing；Then with Ludox (30wt%), sesbania powder according to 1:20:0.02 mass ratio
It is mixed into the slurries of 35wt% with deionized water, Ludox mixed atomizing is into 30~70 μm of microballoon, wherein Ti-MWW molecules
Sieve accounts for the 90wt% of microsphere solid content, microballoon is roasted 10 hours in 550 DEG C, obtained Ti-MWW zeolite products can be used
Make the catalyst of propylene ring oxidation reaction, be denoted as VS-1.
Embodiment 1
This example demonstrates that the preparation method of composite magnetic Ti-MWW molecular sieve catalyst microballoons
(1) by superparamagnetism NiFe2O4Material powder is with Ludox (30wt%), sesbania powder according to 1:20:0.02 mass ratio
The slurries of 35wt% are mixed into deionized water, are then being prepared into 50~70 microns of SiO using spray drying process2Packet
The NiFe wrapped up in2O4Magnetic microsphere NiFe2O4@SiO2, then 500 DEG C of roasting 6h are spare.
(2) at room temperature butyl titanate (TBOT) according to 1:2 mass ratio is added drop-wise to the H of 35% concentration2O2Solution in,
And stir 1 hour simultaneously, obtain the clear Ti solution of yellow.Solution of the boric acid under stiring with above-mentioned Ti is mixed,
And add in the NiFe that (1) obtains2O4@SiO2Magnetic microsphere adds in above-mentioned mixed liquor as silicon source and piperidines (PI), is stirred
Even, obtaining the following material molar ratios of mix slurry is：SiO2：0.026TiO2：1.0B2O3：1.4PI：50H2O is placed in 500ml
Crystallizing kettle Teflon liner in, static state heats 170 DEG C of crystallization 7 days.
(3) in 105 DEG C of dryings, 4h is roasted at 500 DEG C for the solid product deionized water washing and filtering that will be obtained in (2)
Template is removed, obtains NiFe2O4@Si-Ti-MWW molecular sieve initial samples, the HNO with 2mol/L concentration3Solution is according to quality
Frequently 1：50 carry out back flow reaction, remove the B in skeleton outer Ti and skeleton.This acid processing sample roasts 6 hours for 550 DEG C again,
Obtain NiFe2O4@Si-Ti-MWW molecular sieve catalyst microspheres products, are denoted as A.
Embodiment 2~4
This example demonstrates that the preparation method of composite magnetic Ti-MWW molecular sieve catalyst microballoons
Embodiment preparation catalyst process method is same as Example 1, except that the material of selection superparamagnetism has
Difference, mole composition of template and crystallization precursor solution employed in synthesis also difference, it is specific as shown in table 1.
Table 1
Embodiment 5~9
These embodiments explanation uses different magnetic coupling Ti-MWW molecular sieve catalysts, process provided by the invention
There is good propylene ring oxidation reaction effect.For the sake of comparing, by VS-1 catalyst prepared by comparative example 1 there is no magnetic
Contrast test is carried out under conditions of, acquired results are as shown in table 2.
It is 50~70 microns to be packed into 100 milligrams of granularities in 16 millimeters of internal diameter, a height of 300 millimeters of reactor in experiment
Different catalysts；Four internal diameters are 60 millimeters, outer diameter is 165 millimeters, are highly 50 millimeters, the coil edge reaction that the number of turn is 390
Device axial arranging is to provide the distance between uniform magnetic field, coil as 25 millimeters；By the H of a concentration of 30.0wt%2O2Solution and second
In nitrile solvent Mixed design to preheater, a concentration of 65wt% wherein in acetonitrile mixture, and the propylene with coming from gas cylinder mixes
Close heating, propylene and H2O2Molar ratio for 4.1, then entered by magnetically stabilized bed reactor lower part, go out product epoxy third from overhead stream
Alkane (PO).Air in reactor is changed with propylene three times, be then warming up to 45 DEG C, be continuously passed through H when starting experiment2O2, solvent and
Propylene reacts.300 oersted of reactor magnetic field intensity (Oe), reaction pressure 3.0MPa, using propylene calculate weight space velocity as
5.0h-1, react sampling analysis after 2h.
Table 2
| Embodiment | Catalyst | Magnetic field intensity/Oe | PO yields/% | PO selectivity/% | H2O2Conversion ratio/% | H2O2Utilization rate/% |
| Embodiment 5 | A | 300 | 92.5 | 99.7 | 98.1 | 95.6 |
| Embodiment 6 | B | 300 | 92.4 | 99.8 | 98.5 | 94.8 |
| Embodiment 7 | C | 300 | 93.2 | 99.9 | 98.5 | 95.6 |
| Embodiment 8 | D | 300 | 92.7 | 99.6 | 99.0 | 95.7 |
| Embodiment 9 | VS-1 | 0 | 83.8 | 96.2 | 84.2 | 86.9 |
From Table 2, it can be seen that stablized in 5~9 in embodiment using magnetic coupling Ti-MWW molecular sieve catalysts in magnetic
In bed, relative to the VS-1 catalyst that comparative example 1 is used to prepare in embodiment 9, propylene oxide (PO) yield>92%th, epoxy third
Alkane selectivity>99%th, H2O2Conversion ratio and H2O2Effective rate of utilization is respectively>98% He>94%, index parameter, which has, significantly to be changed
It is kind.
Embodiment 10~14
These embodiments illustrate that under different reaction temperatures process provided by the invention has good propylene ring
Oxidation reaction effect.
The magnetic coupling Ti-MWW molecular sieve catalysts A prepared in embodiment using embodiment 1, magnetic stablizing bed design ruler
It is very little identical with embodiment 5~9, the H of addition2O2, the proportionate relationship of acetonitrile solvent and propylene it is also identical with embodiment 5~9, start
Air in reactor is changed with propylene three times, be continuously passed through H during experiment2O2, acetonitrile and propylene reaction react at different temperatures.
300 oersted of reactor magnetic field intensity, reaction pressure 3.0MPa, the weight space velocity calculated using propylene is 5.0h-1, taken after running 2h
Sample is analyzed.
Table 3
Embodiment 15~18
These embodiments illustrate that under different reaction pressures process provided by the invention has good propylene ring
Oxidation reaction effect.
The magnetic coupling Ti-MWW molecular sieve catalysts A prepared in embodiment using embodiment 1, magnetic stablizing bed design ruler
It is very little identical with embodiment 5~9, the H of addition2O2, the proportionate relationship of acetonitrile solvent and propylene it is also identical with embodiment 5~9, start
Air in reactor is changed with propylene three times, be continuously passed through H during experiment2O2, acetonitrile and propylene reaction reacted at 45 DEG C.Reaction
300 oersted of device magnetic field intensity, differential responses pressure, the weight space velocity calculated using propylene is 5.0h-1, run sampling point after 2h
Analysis.
Table 4
| Embodiment | Pressure/Mpa | PO yields/% | PO selectivity/% | H2O2Conversion ratio/% | H2O2Utilization rate/% |
| Embodiment 15 | 1 | 92.9 | 99.6 | 98.9 | 95.2 |
| Embodiment 16 | 2 | 92.1 | 99.8 | 99.0 | 95.7 |
| Embodiment 17 | 3 | 92.5 | 99.7 | 98.1 | 95.6 |
| Embodiment 18 | 5 | 92.3 | 99.7 | 98.2 | 95.1 |
Embodiment 19~25
These embodiments illustrate that under different unstrpped gas volume space velocities process provided by the invention has very well
Propylene ring oxidation reaction effect.
The magnetic coupling Ti-MWW molecular sieve catalysts A prepared in embodiment using embodiment 1, magnetic stablizing bed design ruler
It is very little identical with embodiment 5~9, the H of addition2O2, the proportionate relationship of acetonitrile solvent and propylene it is also identical with embodiment 5~9, start
Air in reactor is changed with propylene three times, be continuously passed through H during experiment2O2, acetonitrile and propylene reaction reacted at 45 DEG C.Reaction
300 oersted of device magnetic field intensity, reaction pressure 3.0MPa, the 1.0~8.0h of weight space velocity range calculated with propylene-1, run 2h
Sampling analysis afterwards.
Table 5
| Embodiment | Air speed/h-1 | PO yields/% | PO selectivity/% | H2O2Conversion ratio/% | H2O2Utilization rate/% |
| Embodiment 19 | 1.0 | 92.5 | 99.7 | 98.4 | 94.4 |
| Embodiment 20 | 2.0 | 92.3 | 99.8 | 98.2 | 93.2 |
| Embodiment 21 | 3.0 | 92.5 | 99.8 | 98.2 | 94.4 |
| Embodiment 22 | 4.0 | 93.0 | 99.6 | 98.3 | 94.2 |
| Embodiment 23 | 6.0 | 92.9 | 99.6 | 98.0 | 95.8 |
| Embodiment 24 | 7.0 | 92.1 | 99.8 | 98.9 | 93.7 |
| Embodiment 25 | 8.0 | 92.9 | 99.9 | 98.3 | 94.7 |
Embodiment 26~30
These embodiments illustrate that under different magnetic field intensities process provided by the invention has good propylene ring
Oxidation reaction effect.The magnetic coupling Ti-MWW molecular sieve catalysts A prepared in embodiment using embodiment 1, it is magnetic stablizing bed
Design size is identical with embodiment 5~9, the H of addition2O2, acetonitrile solvent and propylene proportionate relationship also with 5~9 phase of embodiment
Together, air in reactor is changed with propylene three times, be continuously passed through H when starting experiment2O2, acetonitrile and propylene reaction it is anti-at 45 DEG C
It should.Reactor magnetic field intensity range is in 100~500 oersteds, reaction pressure 3.0MPa, using the weight space velocity that propylene calculates as
5.0h-1, run sampling analysis after 2h.
Table 6
| Embodiment | Magnetic field intensity/Oe | PO yields/% | PO selectivity/% | H2O2Conversion ratio/% | H2O2Utilization rate/% |
| Embodiment 26 | 100 | 93.1 | 99.6 | 98.0 | 93.3 |
| Embodiment 27 | 200 | 92.6 | 99.6 | 98.2 | 94.1 |
| Embodiment 28 | 400 | 92.8 | 99.6 | 99.0 | 94.8 |
| Embodiment 29 | 450 | 92.4 | 99.7 | 98.8 | 93.5 |
| Embodiment 30 | 500 | 92.3 | 99.8 | 98.7 | 93.6 |
The magnetic coupling Ti-MWW molecular sieve catalyst A that embodiment 10~30 shown in table 3~6 is prepared using embodiment 1,
It is being reacted under magnetic stablizing bed different technology conditions as a result, these results illustrate the present invention magnetic coupling Ti-MWW molecular sieves
The magnetic stablizing bed technique of catalyst complex is more than 92%, H to the yield of propylene ring oxidation reaction process oxypropylene2O2Utilization rate
More than 93%, there is the good impact of performance.
The embodiment only technical concepts and features to illustrate the invention, its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of production method of propylene oxide, it is characterised in that：Magnetic field intensity for 100~1000 oersteds it is magnetic stablizing bed in
Under conditions of temperature is 25~100 DEG C and pressure is 0.5~10.0MPa, by propylene, H2O2Solution, organic solvent and compound magnetic
Property Ti-MWW molecular sieve catalysts haptoreactions generation propylene oxide, propylene weight air speed is 0.1~15h-1；
The organic solvent is selected from alcohols, ketone compounds, ether compound, ester type compound, nitrile compounds, hydrocarbon or halogenated
The organic solvent of hydrocarbon；
The composite magnetic Ti-MWW molecular sieve catalysts are using inorganic particle material as kernel, and Ti-MWW molecular sieves are outer
Shell.
2. according to the method described in claim 1, it is characterized in that：Magnetic stablizing bed middle reaction condition is：35~65 DEG C, 0.5~
5.0MPa, 0.5~8.0h of propylene weight air speed-1, 100~500 oersted of magnetic field intensity.
3. method according to claim 1, wherein organic solvent are acetonitrile, acetone, propionitrile, 1,2- dichloroethanes or methanol.
4. according to the method described in claim 1, it is characterized in that：Total weight based on liquid feed stream, organic solvent contain
It measures as 50~75wt%, H2O2Content is 6~28wt%；Propylene and H2O2Molar ratio be 2.0~5.0.
5. according to the method described in claim 1, its characteristic is：Composite magnetic Ti-MWW molecular sieve catalyst preparation methods
For：Inorganic particle material and Ludox, pore-foaming agent, deionized water are mixed into 25~50wt% slurries spray drying formings
Obtain 30~100 microns of magnetic microsphere particles；Titanium source solution according to H2O2Solution quality ratio is 1:(2~8) are added drop-wise to a concentration of
25~50% H2O2In solution, and it is stirred to obtain Ti solution, then boron source is added to be stirred to obtain mixed liquor simultaneously；Then will
Obtained magnetic microsphere adds in above-mentioned mixed liquor as silicon source and organic amine template OSDA, is uniformly mixed, is mixed
Following compositions molar ratio is in object slurries：SiO2：(0.017~0.033) TiO2：(0.2~1.5) B2O3：(0.05~5.0)
OSDA：(20~150) H2O, crystallization 2~14 days at 150~200 DEG C, filtered, washing, dry and 450~650 DEG C of roastings
It obtains composite magnetic Ti-MWW molecular screen primary powders, then original powder and acid processing is removed outside skeleton in Ti and skeleton after B element, then is passed through
500~700 DEG C of roastings obtain composite magnetic Ti-MWW molecular sieve catalysts in 3~20 hours.
6. method according to claim 1 or 5, it is characterised in that：Inorganic particle material is Fe3O4、γ-Fe2O3、
NiFe2O4、CuFe2O4One or more of.
7. according to the method described in claim 6, used pore-foaming agent includes：Sesbania powder, methylcellulose, polymethyl
Acid esters, polyvinylpyrrolidone, PolyTHF, polyisobutene, polyethylene oxide, polystyrene, polyamide, polyacrylate
In it is any.
8. according to the method described in claim 6, the titanium source be tetralkyl titanate, halogenated titanium or titanium oxide, it is described
Silicon source be silica, Ludox or ethyl orthosilicate, the boron source be boric acid or borate, the organic amine template
For piperidines or hexamethylene imine.
9. according to the method described in claim 6, the acid processing procedure is composite Ti-MWW molecular screen primary powders and a concentration of 0.1
~5.0mol/L acid solutions are 1 according to weight ratio：(5~100) it mixes, is handled 0.5~72 hour in 50~200 DEG C, filtered,
Washing, drying, obtain acid-treated product；The acid be inorganic acid or organic acid, inorganic acid be selected from hydrochloric acid, sulfuric acid, nitric acid or
Phosphoric acid, organic acid are selected from formic acid, acetic acid, propionic acid, citric acid or tartaric acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897016A (en) * | 2019-03-18 | 2019-06-18 | 中触媒新材料股份有限公司 | A kind of method that serialization prepares epoxychloropropane |
| WO2021047055A1 (en) * | 2019-09-14 | 2021-03-18 | 南京延长反应技术研究院有限公司 | Etherification-free system and process for preparing epoxypropane by strengthening propylene epoxidation |
| CN113861025A (en) * | 2021-10-29 | 2021-12-31 | 山东徳瑞高分子材料股份有限公司 | Continuous production method of hydroxypropyl methacrylate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5646314A (en) * | 1994-11-16 | 1997-07-08 | Arco Chemical Technology, L.P. | Process for titanium silicalite-catalyzed epoxidation |
| WO2003093255A1 (en) * | 2002-05-02 | 2003-11-13 | Degussa Ag | Process for the epoxidation of olefins |
| WO2011119217A1 (en) * | 2010-03-25 | 2011-09-29 | Dow Global Technologies Llc | Process for producing propylene oxide using a pretreated epoxidation catalyst |
| WO2012048529A1 (en) * | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Method for producing oxidized olefin through olefin epoxidation |
| WO2012076543A1 (en) * | 2010-12-07 | 2012-06-14 | Basf Se | Process for the production of propylene oxide |
| CN106632148A (en) * | 2016-12-27 | 2017-05-10 | 中触媒新材料股份有限公司 | Device and method for preparing propylene oxide |
| US9725428B2 (en) * | 2013-07-24 | 2017-08-08 | Basf Se | Process for preparing propylene oxide |
-
2017
- 2017-12-29 CN CN201711469399.8A patent/CN108191794B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5646314A (en) * | 1994-11-16 | 1997-07-08 | Arco Chemical Technology, L.P. | Process for titanium silicalite-catalyzed epoxidation |
| WO2003093255A1 (en) * | 2002-05-02 | 2003-11-13 | Degussa Ag | Process for the epoxidation of olefins |
| WO2011119217A1 (en) * | 2010-03-25 | 2011-09-29 | Dow Global Technologies Llc | Process for producing propylene oxide using a pretreated epoxidation catalyst |
| WO2012048529A1 (en) * | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Method for producing oxidized olefin through olefin epoxidation |
| WO2012076543A1 (en) * | 2010-12-07 | 2012-06-14 | Basf Se | Process for the production of propylene oxide |
| US9725428B2 (en) * | 2013-07-24 | 2017-08-08 | Basf Se | Process for preparing propylene oxide |
| CN106632148A (en) * | 2016-12-27 | 2017-05-10 | 中触媒新材料股份有限公司 | Device and method for preparing propylene oxide |
Non-Patent Citations (1)
| Title |
|---|
| ZONG BAONING ET AL.: "Magnetically stabilized bed reactors", 《CHINESE JOURNAL OF CATALYSIS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897016A (en) * | 2019-03-18 | 2019-06-18 | 中触媒新材料股份有限公司 | A kind of method that serialization prepares epoxychloropropane |
| WO2021047055A1 (en) * | 2019-09-14 | 2021-03-18 | 南京延长反应技术研究院有限公司 | Etherification-free system and process for preparing epoxypropane by strengthening propylene epoxidation |
| CN113861025A (en) * | 2021-10-29 | 2021-12-31 | 山东徳瑞高分子材料股份有限公司 | Continuous production method of hydroxypropyl methacrylate |
| CN113861025B (en) * | 2021-10-29 | 2022-12-30 | 山东徳瑞高分子材料股份有限公司 | Continuous production method of hydroxypropyl methacrylate |
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