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CN108191794B - Propylene epoxidation reaction method - Google Patents

Propylene epoxidation reaction method Download PDF

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CN108191794B
CN108191794B CN201711469399.8A CN201711469399A CN108191794B CN 108191794 B CN108191794 B CN 108191794B CN 201711469399 A CN201711469399 A CN 201711469399A CN 108191794 B CN108191794 B CN 108191794B
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propylene
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mww molecular
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CN108191794A (en
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王志光
李进
王炳春
王建青
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Dalian Heterogeneous Catalyst Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
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Abstract

The invention discloses a propylene epoxidation method, which comprises the steps of reacting propylene, a solvent and H in a magnetically stabilized bed reactor 2O 2The mixture is in contact reaction with a magnetic Ti-MWW molecular sieve catalyst, the temperature is 25-100 ℃, the pressure is 0.1-10.0 MPa, and the weight space velocity of propylene is 0.1-15 h ‑1And reacting under the condition that the magnetic field intensity is 100-1000 oersted to convert propylene into propylene oxide. The product propylene oxide of the reaction has a yield and selectivity of greater than 92% and greater than 98%, respectively, H 2O 2The conversion rate and the utilization rate are respectively more than 98 percent and more than 93 percent, the product quality is improved, the reaction efficiency is also improved, and the separation and purification cost is reduced. Compared with the fluidized bed process, the bubble is broken by the magnetic field, so the mass transfer efficiency is high, the catalyst is less taken out, the energy consumption is reduced, the environmental pollution is reduced, and the processing capacity of the device is improved.

Description

Propylene epoxidation reaction method
Technical Field
The invention belongs to a preparation method of a known compound, and particularly relates to a method for preparing propylene oxide by catalyzing propylene epoxidation reaction in a magnetic stabilization bed by using a composite magnetic Ti-MWW molecular sieve.
Background
Propylene Oxide (PO) is an important bulk chemical raw material, has active chemical property and wide application because of having an oxygen-containing three-membered ring with very large tension, and is mainly used for producing polyether, further producing polyurethane plastics, foam stabilizers, defoaming agents in the paper industry, crude oil demulsifiers, oil well acid treatment wetting agents, high-efficiency low-foam detergents and the like. Propylene oxide is also used to produce propylene glycol, and thus unsaturated polyester resins, and the like. With the expansion of the application of the propylene oxide and the continuous increase of the consumption of downstream products, particularly the flourishing of industries such as automobiles, buildings, home furnishings and the like, the demand of polyurethane and nonionic surfactants is greatly increased, and the market demand of the propylene oxide is vigorous.
At present, the industry of propylene oxide is worldwideThe production method mainly comprises chlorohydrination method, co-oxidation method (also called co-production method and indirect oxidation method), cumene oxidation method (CHP method) and H 2O 2The direct oxidation method (HPPO method), wherein the HPPO method is the key point of the present research and development because of environmental protection and no pollution, and tends to mature, thus showing good industrialization prospect. The TS-1 and Ti-MWW molecular sieve can be used as a new process (HPPO) catalyst for preparing propylene oxide from propylene. The optimal solvents in the HPPO process are methanol and acetonitrile respectively, and the main product is propylene oxide.
Patent CN103724299B discloses that n fixed bed reactors connected in series are used for propylene epoxidation, and the raw materials sequentially enter the fixed bed reactors connected in series according to the material flow direction, and contact with the catalyst of the TS-1 type titanium silicalite molecular sieve in each reactor to generate a product containing propylene oxide. The reaction temperature of each reactor arranged in series according to the flowing direction of the raw materials is gradually decreased. Patent CN101941954B describes a fixed bed reactor for H, in which a catalyst bed is divided into n sections of an integer of 2 or more 2O 2And propylene to propylene oxide.
Patent CN104130216B developed a H 2O 2The direct oxidation propylene/propane mixed gas adopts a fluidized bed loop reactor to continuously produce the propylene oxide. In the process, the slurry discharged from a flash tower respectively evaporates low-oxygen propylene/propane mixed gas and propylene oxide, mother liquor containing the catalyst is separated into fine particle molecular sieve catalyst slurry and mother liquor by a membrane separator, the mother liquor is subjected to flash evaporation to separate methanol, recovered solvent methanol is utilized to synchronously recover residual high-oxygen propylene/propane mixed gas after reaction in a high-oxygen propylene/propane absorption tower and recycle the high-oxygen propylene/propane mixed gas, and the catalyst slurry returns to a reactor for recycling after on-line partial regeneration.
Patent CN101456849B develops a method and a device for preparing propylene oxide by using carbon dioxide as a reaction medium to catalyze propylene epoxidation under supercritical conditions. Adding a large-particle-size TS-1 catalyst, adding a gaseous reactant propylene into a mixer, and adding a liquid reactant H into the mixer 2O 2The water solution and the cosolvent methanol and carbon dioxide are introduced into a mixer and are mixed with propylene and H 2O 2The aqueous solution and the cosolvent methanol are mixed and then enter a reactor for reaction to obtain a reaction product propylene oxide.
Disclosure of Invention
The invention aims to solve the problem that the reaction performance is influenced by overhigh pressure drop of a fixed bed, channeling and local overheating in the conventional propylene epoxidation reaction, also solves the problem of the reduction of the catalytic performance caused by the phenomena of interphase back mixing and particle loss of a fluidized bed, develops a novel process method combining a magnetically stabilized bed and a composite magnetic Ti-MWW molecular sieve catalyst, and improves the activity of propylene conversion and the selectivity of products.
The magnetically stabilized bed used in the present invention is a new type of reaction bed, combining many of the advantages of both fixed and fluidized beds. Compared with a fluidized bed, the external magnetic field can effectively control the phenomena of interphase back mixing and particle loss; compared with the fixed bed, the magnetically stabilized bed can use small particle catalyst without causing too high pressure drop, and the uniform void degree can make the bed layer not suitable for generating channeling and local overheating. In addition, the magnetically stabilized bed can be operated stably in a wide range, and can break up bubbles to improve mass transfer between phases. The magnetically stabilized bed with the characteristics has good application prospect in propylene epoxidation reaction. However, to fully exert the advantages, the catalyst must have the magnetic response characteristic, and the invention also provides a composite magnetic Ti-MWW molecular sieve catalyst which can be well matched with a magnetic stable bed to form a combined innovative process method and has good application prospect.
The invention provides a method for producing propylene oxide, which is characterized by comprising the following steps: under the conditions of temperature of 25-100 ℃ and pressure of 0.5-10.0 MPa, propylene and H are mixed in a magnetic stabilization bed with magnetic field intensity of 100-1000 oersted 2O 2The solution, the organic solvent and the composite magnetic Ti-MWW molecular sieve catalyst are contacted and reacted to generate the propylene oxide, wherein the weight space velocity of the propylene is 0.1-15 h -1。
The magnetic stabilization bed reactor consists of a reactor and an external magnetic field, wherein the external magnetic field is a uniform stabilization magnetic field along the axial direction of the reactor, the uniform magnetic field is provided by a direct current power supply and a Helmholtz coil or a uniform tightly wound solenoid which are coaxial with the reactor, and a catalyst with ferromagnetism is mutually attracted and stably exists in the reactor due to the magnetization effect of the magnetic field.
In the present invention, the reaction is carried out in the presence of an organic solvent. Useful organic solvents include organic compounds such as alcohols (methanol, t-butanol, etc.), ketones (acetone, etc.), ethers (1, 4-dioxane, etc.), esters (methyl acetate, ethyl acetate, etc.), nitriles (acetonitrile, propionitrile, etc.), hydrocarbons (n-heptane, toluene, etc.), halogenated hydrocarbons (1, 2-dichloroethane, etc.), and the like.
The composite magnetic Ti-MWW molecular sieve catalyst takes inorganic magnetic particle materials as an inner core and Ti-MWW molecular sieves as outer shells.
The reaction conditions in the magnetically stabilized bed of the present invention are preferably: 35-65 ℃, 0.5-5.0 MPa and the propylene weight space velocity of 0.5-8.0 h -1And the magnetic field intensity is 100-500 oersted.
The organic solvent used in the epoxidation reaction of propylene is preferably acetonitrile, acetone, propionitrile, 1, 2-dichloroethane, or toluene, and more preferably acetonitrile.
The reaction process of the invention is characterized in that: based on the total weight of the liquid feed stream, the acetonitrile content is 60-75 wt%, H 2O 2The content is 7-28 wt%; propylene and H 2O 2The molar ratio of (A) to (B) is 2.0-5.0;
the magnetic composite catalyst material of the invention has the inorganic magnetic particle material of the kernel of Fe 3O 4、γ-Fe 2O 3、NiFe 2O 4、CuFe 2O 4One or more of them.
The preparation method of the composite magnetic Ti-MWW molecular sieve catalyst is characterized by comprising the following steps: mixing an inorganic magnetic particle material with silica sol, a pore-forming agent and deionized water to obtain 25-50 wt% of slurry, and carrying out spray drying and forming to obtain 30-100 micron microsphere particles; titanium source solution is reacted with H 2O 2The solution is added into H with the concentration of 25-50% dropwise in a mass ratio of 1 (2-10) 2O 2Adding into the solution, stirring and mixing to obtain Ti solution, adding boron source, stirring and mixingObtaining a mixed solution; then adding the obtained magnetic microspheres and an organic amine template (OSDA) agent into the mixed solution, and uniformly stirring and mixing to obtain a mixture slurry with the following molar composition: SiO 2 2：(0.017～0.033)TiO 2：(0.2～1.5)B 2O 3：(0.05～5.0)OSDA：(20～150)H 2And crystallizing the O at 150-200 ℃ for 2-14 days, filtering, washing, drying and roasting at 450-650 ℃ to obtain composite magnetic Ti-MWW molecular sieve raw powder, treating the raw powder with inorganic acid to remove Ti outside a framework and B elements in the framework, and roasting at 500-700 ℃ for 3-20 hours to obtain the composite magnetic Ti-MWW molecular sieve catalyst.
The porogenic agent used in the synthetic process comprises the following components: sesbania powder, methylcellulose, polymethacrylate, polyvinylpyrrolidone, polytetrahydrofuran, polyisobutylene, polyethylene oxide, polystyrene, polyamide and polyacrylate.
In the synthesis process, the titanium source is tetraalkyl titanate, titanium halide or titanium oxide, the silicon source is silicon dioxide, silica sol or tetraethoxysilane, the boron source is boric acid or borate, and the organic amine template agent is piperidine or hexamethyleneimine.
In the synthetic process, the composite Ti-MWW molecular sieve raw powder and an acidic solution with the concentration of 0.1-5.0 mol/L are mixed according to the weight ratio of 1: (5-100) preparing a reaction mixture, wherein the acid is an inorganic acid or an organic acid, the inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, the organic acid is formic acid, acetic acid, propionic acid, citric acid or tartaric acid, treating for 0.5-72 hours at 50-200 ℃, and filtering, washing and drying to obtain an acid treatment product.
The preparation method of the composite magnetic Ti-MWW molecular sieve catalyst is characterized by comprising the following steps: mixing an inorganic magnetic particle material with silica sol, a pore-forming agent and deionized water to obtain 25-50 wt% of slurry, and carrying out spray drying and forming to obtain 30-100 micron microsphere particles; then mixing with a titanium source, a boron source and a template agent for crystallization to obtain composite magnetic Ti-MWW molecular sieve raw powder, treating the dried and roasted raw powder with inorganic acid to remove Ti outside a framework and B element in the framework, and obtaining the composite magnetic Ti-MWW molecular sieve catalyst.
The pore-foaming agent used in the preparation method comprises the following components: sesbania powder, methylcellulose, polymethacrylate, polyvinylpyrrolidone, polytetrahydrofuran, polyisobutylene, polyethylene oxide, polystyrene, polyamide and polyacrylate.
The magnetically stabilized bed reactor consists of reactor and externally applied magnetic field, the externally applied magnetic field is one homogeneous stable magnetic field along the axial direction of the reactor and is provided with DC power supply and a series of Helmholtz coils or homogeneously wound solenoid coils coaxial with the reactor, and the reactor and other parts are made of material with excellent magnetic permeability.
The on-line loading and unloading method of the catalyst comprises the following steps: preparing slurry of fine-particle fresh catalyst in a catalyst preparation kettle by using a reaction solvent, pumping the slurry into the upper part of a magnetic stabilization bed by using a catalyst feeding pump, and retaining the catalyst in the magnetic stabilization bed reactor under the action of a magnetic field; and continuously or intermittently discharging the slurry of the deactivated catalyst and the materials at the bottom of the magnetic stabilization bed reactor out of the magnetic stabilization bed reactor from a catalyst discharge port at the bottom of the magnetic stabilization bed for solid-liquid separation to separate out solid waste catalyst, and recycling the liquid.
The particle size of the catalyst in the method provided by the invention can be 30-100 microns, the preferable particle size is 30-70 microns, and the catalyst particles can be independently placed in a magnetic stable bed reactor. The catalyst can be fixedly present in the reactor, and can also be continuously or intermittently fed into and discharged from the reactor according to the operation requirement.
Compared with the prior fluidized bed or fixed bed HPPO process, the method provided by the invention has the advantages that because a magnetic stabilized bed reactor and a composite magnetic Ti-MWW molecular sieve catalyst are used, the method has the following advantages:
(1) compared with the prior fixed bed reactor process, the method has the advantages of reduced bed lamination, high mass transfer efficiency and less side reaction; compared with the common fluidized bed reactor process, the magnetic field breaks bubbles, so that the mass transfer efficiency is high and the catalyst is less taken out. The catalyst consumption is low, the catalyst and the reaction materials do not need to be separated, the process is simple, the operation is convenient, and the catalyst can be conveniently loaded and unloaded and regenerated outside the reactor under the action of an external magnetic field; meanwhile, the method has the advantages of wide operation range, high space velocity of reactant flow, high mass transfer and heat transfer efficiency of reaction and the like.
(2) The magnetic composite molecular sieve catalyst with small grain size is used, the reaction efficiency is improved, the propylene conversion rate and the product selectivity are respectively more than 92 percent and 99 percent, and H 2O 2The conversion rate and the effective utilization rate of the product are respectively more than 98 percent and 93 percent, the product quality is improved, and the cost of subsequent product purification is also saved.
The catalyst with fine particles (<0.15mm) is used in the magnetically stabilized bed reactor without increasing the pressure drop of the bed layer, and compared with the catalyst with large particles (>0.8mm) used in the slurry bed reactor, the method greatly improves the effect of gas-solid phase mass and heat transfer, thereby reducing the apparent energy consumption.
Because the catalyst used is fine, the catalyst can be loaded and unloaded at any time during the process of the invention to carry out the regeneration outside the reactor without stopping the operation of the whole device.
Drawings
The invention is further described with reference to the following figures and examples:
FIG. 1: a process flow diagram of the magnetic stabilization bed;
in the figure, 1, a raw material pump, 2, a preheater, 3, a magnetic stabilization bed, 4, a magnetic coil, 5, a cooler, 6, a separator, 7 and a magnetic strength controller.
Detailed Description
The embodiments and the effects of the present invention are further illustrated by the examples and comparative examples, but the scope of the present invention is not limited to the contents listed in the examples.
H is calculated by the following calculation formula 2O 2Conversion, PO (propylene oxide) selectivity, H 2O 2Effective utilization rate, C 3H 6(propylene) conversionConversion rate and PO yield.
H 2O 2Conversion rate:
Figure BDA0001531700910000071
PO selectivity:
H 2O 2effective utilization rate:
C 3H 6conversion rate:
yield of PO:
Figure BDA0001531700910000075
in the formula C 0 H2O2And C i H2O2Mass concentration of hydrogen peroxide before and after reaction, n 0 C3H6And n i C3H6Respectively the mole number of propylene before and after the reaction, n 0 H2O2And n i H2O2Hydrogen peroxide H before and after reaction 2O 2Mole number of (2), n po，n NMEAnd n PGThe amounts of propylene oxide, propylene glycol monomethyl ether and propylene glycol produced after the reaction, respectively. As an index for evaluating the reactivity, X H2O2，S po，Y poAfter reaction for 6 hours, the samples are measured every 2 hours, so that the errors of three indexes of the sample measurement results of three continuous samples are less than 2%, and meanwhile, the average value of the results of the three samples is used as the index of the reaction performance.
Comparative example 1
Ti-MWW molecular sieves were synthesized according to the literature (J.Phys. chem. B,2001,105(15), 2897-2905).
TiO in titanium source by mole ratio 2: SiO in silicon source 2: b in boron source 2O 3: f-in the fluorine source: organic template agent: h 2O is 0.033: 1: 0.67: 1: 1.4: 19 preparing a reaction mixture, wherein the titanium source is tetrabutyl titanate, the silicon source is silica gel, the boron source is boric acid, the fluorine source is HF, the organic template agent is piperidine, and the reaction mixture is subjected to hydrothermal crystallization at 170 ℃ for 7 days, and is filtered, washed and dried to obtain Ti-MWW molecular sieve raw powder; mixing Ti-MWW molecular sieve raw powder and a nitric acid solution with the concentration of 2mol/l according to the weight ratio of 1: 50 preparing a reaction mixture, treating the reaction mixture at 100 ℃ for 20 hours, and filtering, washing and drying the reaction mixture to obtain a product after acid treatment; and mixing the titanium-tungsten-molybdenum composite powder with silica sol (30 wt%) and sesbania powder and deionized water according to the mass ratio of 1:20:0.02 to obtain 35 wt% of slurry, mixing the silica sol and spraying the slurry into microspheres of 30-70 mu m, wherein the Ti-MWW molecular sieve accounts for 90 wt% of the solid content of the microspheres, roasting the microspheres at 550 ℃ for 10 hours, and obtaining a Ti-MWW molecular sieve product which can be used as a catalyst for propylene epoxidation and is marked as VS-1.
Example 1
This example illustrates the preparation of composite magnetic Ti-MWW molecular sieve catalyst microspheres
(1) Mixing the superparamagnetic NiFe 2O 4Mixing the material powder, silica sol (30 wt%), sesbania powder and deionized water according to the mass ratio of 1:20:0.02 to form 35 wt% of slurry, and preparing the slurry into 50-70 micron SiO by using a spray drying method 2Encapsulated NiFe 2O 4Magnetic microsphere NiFe 2O 4@SiO 2Then roasting for 6h at 500 ℃ for standby.
(2) Tetrabutyl titanate (TBOT) is dripped into H with the concentration of 35% according to the mass ratio of 1:2 at room temperature 2O 2While stirring for 1 hour, to give a yellow clear Ti solution. Mixing boric acid and the Ti solution under stirring, and adding the NiFe obtained in the step (1) 2O 4@SiO 2Adding magnetic microspheres serving as a silicon source and Piperidine (PI) into the mixed solution, and uniformly stirring and mixing to obtain a mixture slurry, wherein the mixture slurry comprises the following raw materials in a molar ratio: SiO 2 2：0.026TiO 2：1.0B 2O 3：1.4PI：50H 2And O, placing the mixture into a Teflon lining of a 500ml crystallization kettle, and statically heating the mixture to 170 ℃ for crystallization for 7 days.
(3) Washing the solid product obtained in the step (2) with deionized water, filtering, drying at 105 ℃, roasting at 500 ℃ for 4h to remove the template agent to obtain NiFe 2O 4Initial sample of @ Si-Ti-MWW molecular sieve, with HNO at concentration of 2mol/L 3The solution is prepared by mixing the following components in a mass ratio of 1: 50, carrying out reflux reaction to remove Ti outside the framework and B in the framework. The acid treated sample was then calcined at 550 ℃ for 6 hours to obtain NiFe 2O 4The product of the @ Si-Ti-MWW molecular sieve catalyst microsphere is marked as A.
Examples 2 to 4
This example illustrates the preparation of composite magnetic Ti-MWW molecular sieve catalyst microspheres
Examples the process for preparing the catalyst was the same as in example 1, except that the materials selected for superparamagnetic property were different, and the molar compositions of the template and the crystallization precursor solution used in the synthesis were also different, as shown in table 1.
TABLE 1
Figure BDA0001531700910000101
Examples 5 to 9
These examples illustrate that the process of the present invention provides good propylene epoxidation using different magnetic composite Ti-MWW molecular sieve catalysts. For comparison, the VS-1 catalyst prepared in comparative example 1 was subjected to a comparative test in the absence of a magnetic field, and the results are shown in table 2.
In the test, a reactor with the inner diameter of 16 mm and the height of 300 mm is filled with 100 mg of different catalysts with the particle size of 50-70 microns; four coils with an inner diameter of 60 mm, an outer diameter of 165 mm, a height of 50 mm and a number of turns of 390 are axially arranged along the reactor to provide a uniform magnetic field, and the distance between the coils is 25 mm; h with a concentration of 30.0 wt% 2O 2Mixing the solution and acetonitrile solvent, and feeding into preheater, wherein the concentration of acetonitrile mixed solution is 65 wt%, and the mixed solution is mixed with propylene from gas cylinderMixing and heating propylene and H 2O 2Is 4.1, and the product Propylene Oxide (PO) flows out from the upper part of the magnetically stabilized bed reactor. At the beginning of the experiment, the air in the reactor was replaced with propylene three times, then the temperature was raised to 45 ℃ and H was continuously fed 2O 2The solvent and propylene. The magnetic field intensity of the reactor is 300 oersted (Oe), the reaction pressure is 3.0MPa, and the weight space velocity calculated by propylene is 5.0h -1And sampling and analyzing after reacting for 2 h.
TABLE 2
Examples Catalyst and process for preparing same Magnetic field intensity/Oe PO yield/%) PO selectivity/%) H 2O 2Conversion rate/% H 2O 2Utilization rate%
Example 5 A 300 92.5 99.7 98.1 95.6
Example 6 B 300 92.4 99.8 98.5 94.8
Example 7 C 300 93.2 99.9 98.5 95.6
Example 8 D 300 92.7 99.6 99.0 95.7
Example 9 VS-1 0 83.8 96.2 84.2 86.9
As can be seen from Table 2, the Propylene Oxide (PO) yields in examples 5-9 using the magnetic composite Ti-MWW molecular sieve catalyst in a magnetically stabilized bed relative to the VS-1 catalyst prepared in comparative example 1 used in example 9>92% selectivity to propylene oxide>99％、H 2O 2Conversion rateAnd H 2O 2The effective utilization ratio is respectively>98% and>94 percent, the index parameters are obviously improved.
Examples 10 to 14
These examples show that the process of the present invention provides a good propylene epoxidation reaction at different reaction temperatures.
In the examples, the magnetic composite Ti-MWW molecular sieve catalyst A prepared in example 1 was used, the design size of the magnetic stabilization bed was the same as in examples 5 to 9, and H was added 2O 2The ratio of acetonitrile solvent to propylene was the same as in examples 5 to 9, and at the start of the experiment, air in the reactor was replaced with propylene three times and H was continuously supplied 2O 2Acetonitrile and propylene were reacted at different temperatures. The magnetic field intensity of the reactor is 300 oersted, the reaction pressure is 3.0MPa, and the weight space velocity calculated by propylene is 5.0h -1And sampling and analyzing after running for 2 h.
TABLE 3
Figure BDA0001531700910000111
Figure BDA0001531700910000121
Examples 15 to 18
These examples show that the process of the present invention provides a good propylene epoxidation reaction at different reaction pressures.
In the examples, the magnetic composite Ti-MWW molecular sieve catalyst A prepared in example 1 was used, the design size of the magnetic stabilization bed was the same as in examples 5 to 9, and H was added 2O 2The ratio of acetonitrile solvent to propylene was the same as in examples 5 to 9, and at the start of the experiment, air in the reactor was replaced with propylene three times and H was continuously supplied 2O 2Acetonitrile and propylene were reacted at 45 ℃. The magnetic field intensity of the reactor is 300 oersted, the weight space velocity calculated by propylene is 5.0h under different reaction pressures -1And sampling and analyzing after running for 2 h.
TABLE 4
Examples pressure/Mpa PO yield/%) PO selectivity/%) H 2O 2Conversion rate/% H 2O 2Utilization rate%
Example 15 1 92.9 99.6 98.9 95.2
Example 16 2 92.1 99.8 99.0 95.7
Example 17 3 92.5 99.7 98.1 95.6
Example 18 5 92.3 99.7 98.2 95.1
Examples 19 to 25
These examples show that the process provided by the present invention has good propylene epoxidation effect under different volume space velocities of raw material gas.
In the examples, the magnetic composite Ti-MWW molecular sieve catalyst A prepared in example 1 was used, the design size of the magnetic stabilization bed was the same as in examples 5 to 9, and H was added 2O 2The ratio of acetonitrile solvent to propylene was the same as in examples 5 to 9, and at the start of the experiment, air in the reactor was replaced with propylene three times and H was continuously supplied 2O 2Acetonitrile and propylene were reacted at 45 ℃. The magnetic field intensity of the reactor is 300 oersted, the reaction pressure is 3.0MPa, and the weight space velocity calculated by propylene is 1.0-8.0 h -1And sampling and analyzing after running for 2 h.
TABLE 5
Examples Space velocity/h-1 PO yield/%) PO selectivity/%) H 2O 2Conversion rate/% H 2O 2Utilization rate%
Example 19 1.0 92.5 99.7 98.4 94.4
Example 20 2.0 92.3 99.8 98.2 93.2
Example 21 3.0 92.5 99.8 98.2 94.4
Example 22 4.0 93.0 99.6 98.3 94.2
Example 23 6.0 92.9 99.6 98.0 95.8
Example 24 7.0 92.1 99.8 98.9 93.7
Example 25 8.0 92.9 99.9 98.3 94.7
Examples 26 to 30
These examples show that the process of the present invention provides a good epoxidation of propene at different magnetic field strengths. In the examples, the magnetic composite Ti-MWW molecular sieve catalyst A prepared in example 1 was used, the design size of the magnetic stabilization bed was the same as in examples 5 to 9, and H was added 2O 2The ratio of acetonitrile solvent to propylene was the same as in examples 5 to 9, and at the start of the experiment, air in the reactor was replaced with propylene three times and H was continuously supplied 2O 2Acetonitrile and propylene were reacted at 45 ℃. The magnetic field intensity of the reactor is within 100-500 oersted, the reaction pressure is 3.0MPa, and the weight space velocity calculated by propylene is 5.0h -1And sampling and analyzing after running for 2 h.
TABLE 6
Examples Magnetic field intensity/Oe PO yield/%) PO selectivity/%) H 2O 2Conversion rate/% H 2O 2Utilization rate%
Example 26 100 93.1 99.6 98.0 93.3
Example 27 200 92.6 99.6 98.2 94.1
Example 28 400 92.8 99.6 99.0 94.8
Example 29 450 92.4 99.7 98.8 93.5
Example 30 500 92.3 99.8 98.7 93.6
Examples 10 to 30 shown in tables 3 to 6 show the results of the reaction of the magnetic composite Ti-MWW molecular sieve catalyst A prepared in example 1 under different process conditions of the magnetically stabilized bed, which show that the yield of propylene oxide in the epoxidation of propylene is more than 92% by matching the magnetic composite Ti-MWW molecular sieve catalyst of the present invention with the magnetically stabilized bed process, and that H is higher than H 2O 2The utilization rate is more than 93%, and the performance effect is good.
The embodiments are only for illustrating the technical concept and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (8)

1. A method for producing propylene oxide, which is characterized by comprising the following steps: under the conditions of temperature of 25-100 ℃ and pressure of 0.5-10.0 MPa, propylene and H are mixed in a magnetic stabilization bed with magnetic field intensity of 100-1000 oersted 2O 2The solution, the organic solvent and the composite magnetic Ti-MWW molecular sieve catalyst are contacted and reacted to generate the propylene oxide, wherein the weight space velocity of the propylene is 0.1-15 h -1；
The organic solvent is selected from organic solvents of alcohols, ketone compounds, ether compounds, ester compounds, nitrile compounds, hydrocarbons or halogenated hydrocarbons;
the composite magnetic Ti-MWW molecular sieve catalyst takes an inorganic magnetic particle material as an inner core and a Ti-MWW molecular sieve as an outer shell;
the preparation method of the composite magnetic Ti-MWW molecular sieve catalyst comprises the following steps: mixing an inorganic magnetic particle material with silica sol, a pore-forming agent and deionized water to obtain 25-50 wt% of slurry, and carrying out spray drying and forming to obtain 30-100 micron magnetic microsphere particles; titanium source solution is reacted with H 2O 2The solution is added into H with the concentration of 25-50% dropwise according to the mass ratio of 1 (2-8) 2O 2Stirring and mixing the Ti solution and the boron source to obtain a mixed solution; then adding the obtained magnetic microspheres as a silicon source and an organic amine template agent OSDA into the mixed solution, and uniformly stirring and mixing to obtain mixture slurry, wherein the mixture slurry comprises the following components in a molar ratio: SiO 2 2：(0.017~0.033)TiO 2：(0.2~1.5)B 2O 3：(0.05~5.0)OSDA：(20~150)H 2And crystallizing the O at 150-200 ℃ for 2-14 days, filtering, washing, drying and roasting at 450-650 ℃ to obtain composite magnetic Ti-MWW molecular sieve raw powder, treating the raw powder with acid to remove Ti outside the framework and B element in the framework, and roasting at 500-700 ℃ for 3-20 hours to obtain the composite magnetic Ti-MWW molecular sieve catalyst.
2. The method of claim 1, wherein: the reaction conditions in the magnetically stabilized bed were: 35-65 ℃, 0.5-5.0 MPa and the propylene weight space velocity of 0.5-8.0 h -1And the magnetic field intensity is 100-500 oersted.
3. The method of claim 1, further comprising: wherein the organic solvent is acetonitrile, acetone, propionitrile, 1, 2-dichloroethane or methanol.
4. The method of claim 1, wherein: the organic solvent content is 50-75 wt%, based on the total weight of the liquid feed stream, H 2O 2The content is 6-28 wt%; propylene and H 2O 2The molar ratio of (A) to (B) is 2.0-5.0.
5. The method of claim 1, wherein: the inorganic magnetic particle material is Fe 3O 4、γ-Fe 2O 3、NiFe 2O 4、CuFe 2O 4One or more of them.
6. The method of claim 1, wherein: the porogens used include: sesbania powder, methylcellulose, polymethacrylate, polyvinylpyrrolidone, polytetrahydrofuran, polyisobutylene, polyethylene oxide, polystyrene, polyamide and polyacrylate.
7. The method of claim 1, wherein: the titanium source is tetraalkyl titanate, titanium halide or titanium oxide, the silicon source is silicon dioxide, silica sol or ethyl orthosilicate, the boron source is boric acid or borate, and the organic amine template agent is piperidine or hexamethyleneimine.
8. The method of claim 5, wherein: the acid treatment process comprises the following steps of mixing composite Ti-MWW molecular sieve raw powder and an acid solution with the concentration of 0.1-5.0 mol/L according to the weight ratio of 1: (5-100), treating for 0.5-72 hours at 50-200 ℃, filtering, washing and drying to obtain an acid treatment product; the acid is inorganic acid or organic acid, the inorganic acid is selected from hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and the organic acid is selected from formic acid, acetic acid, propionic acid, citric acid or tartaric acid.
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Citations (7)

* Cited by examiner, † Cited by third party
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
Magnetically stabilized bed reactors;ZONG Baoning et al.;《Chinese Journal of Catalysis》;20130120;第34卷;第61-68页 *

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