A kind of reactor and the method for preparing expoxy propane using the reactor
Technical field
The present invention is provided a kind of reactor for preparing expoxy propane and is prepared the side of expoxy propane using the reactor
Method.
Background technology
Expoxy propane (expoxy propane) is as a kind of important basic organic chemical raw material, industrial mainly for the preparation of poly-
Ethoxylated polyhydric alcohol, propane diols, hydramine and all kinds of nonionic surfactants, its derivative are widely used in petrochemical industry, building, family
The industries such as electricity, automobile, medicine, agricultural chemicals, weaving, daily use chemicals.However, traditional Synthesis of Propylene Oxide such as chlorohydrination or cooxidation
Method is with pollution weight, corrosion is big, joint product are more, high cost.Therefore, each state is all active development flow process is simple, cleaning
Economic green Producing Process of Propylene Oxide.
SUMITOMO CHEMICAL chemical company develops isopropyl benzene hydroperoxide method (hereinafter referred to as CHP methods) on the basis of conjugated oxidation.
CHP methods adopt isopropyl benzene hydroperoxide to make oxidant, titanium-silicone metapore molecular sieve for catalyst, reacted after prepared expoxy propane and
Dimethyl benzyl alcohol.Dimethyl benzyl alcohol becomes the use of isopropyl benzene hydroperoxide Posterior circle again through dehydration, hydrogenation, oxidation.CHP methods without
Co-product, equipment investment are low, and implementation result is more significant, have been enter into industrialization phase.The technique is to reduce the generation of side reaction, carries
The conversion ratio of high isopropyl benzene hydroperoxide, needs to add substantial amounts of propylene, correspondingly increases equipment operation energy consumption.
Patent CN 1206225C reduces the generation of side reaction by the concentration of water in control isopropyl benzene hydroperoxide solution,
The yield of expoxy propane is improved, when water concentration is reduced to 0.2wt% in isopropyl benzene hydroperoxide solution, isopropyl benzene hydroperoxide turns
It is 99% to change rate, and expoxy propane selection rate is 95%.The method isopropyl benzene hydroperoxide is 1 with the molar feed ratio of propylene:10,
Propylene utilization rate is low.Patent CN1252059C discloses the clean manufacturing side that a kind of low pressure low concentration propylene prepares expoxy propane
Method, using multiphase molybdenum series catalyst, improves the selectivity of expoxy propane, it is to avoid the generation of alkaline waste liquor, isopropyl benzene hydroperoxide
Conversion ratio is 84%, and expoxy propane is selectively 89%.High activity molybdenum base poor catalyst stability that the invention is adopted, volatile
Living, it is difficult to realize industrial applications.Patent CN101619048B discloses one kind and makes hydrogen, oxygen and propylene in closed reactor
In contact with catalyst generate expoxy propane method, by make hydrogen and oxygen prior to propylene enter reaction system, then again
It is passed through hydrogen and oxygen continues reaction, improves the effective rate of utilization of the conversion ratio and hydrogen of propylene.The method is will to use greatly
Improving the conversion ratio of propylene, the conversion ratio of oxygen is very low for the excessive hydrogen and oxygen of width.Patent CN101456849B is disclosed
The method and device of preparing epoxypropane by epoxidation of propene is catalyzed under super critical condition.With supercritical carbon dioxide in the method
For reaction medium, using the TS-1 catalyst of big particle diameter, the hydrogen peroxide of high concentration, propylene and cosolvent methyl alcohol hybrid reaction are obtained
Arrive expoxy propane., using high concentration hydrogen peroxide as oxidant, transport, storage are using all than relatively hazardous for the method;Course of reaction
Cosolvent methyl alcohol need to be added, separating difficulty is increased.
Develop a kind of easily-controlled operation, side reaction few, isopropyl benzene hydroperoxide high conversion rate, expoxy propane are selectively high
Synthesis technique is very necessary.
Content of the invention
The invention provides a kind of reactor for preparing expoxy propane, the reactor can realize 2 kinds of reaction masses
Head-on collision mixing at a high speed, so as to form stable fine particle mixture, strengthens the alternate mixing between reaction mass, strengthens heat transfer and passes
Matter effect, reduces the generation of side reaction, improves isopropyl benzene hydroperoxide conversion ratio and expoxy propane selectivity.
In order to solve the above problems, the technical solution used in the present invention is such:A kind of reactor, in the middle part of the reactor
Epoxidation catalyst is filled with, roof is provided with gas vent, and upper portion side wall is provided with liquid outlet, and lower sides are provided with 1
Or 2 groups of injectors, every group of injector include 2 injectors, and both are distributed in approximately the same plane and mutually symmetrical, described injection
The nozzle that device is connected by jet pipe and with jet pipe is constituted, and described nozzle is conical butt, one end that nozzle is connected with jet pipe
With diameter greater than the diameter away from jet pipe one end, nozzle is stretched in fixed bed reactors, and jet pipe is divided into 2 sections, and jet pipe is away from nozzle
One section is cylinder, and another section is conical butt, and jet pipe is away from nozzle one end with diameter greater than one end for being connected with nozzle
Diameter.
Wherein, in order to realize uniform heat release, beneficial to temperature control, the epoxidation catalyst is divided into upper and lower two-layer and is filled in instead
Answer in the middle part of device, lower floor is catalyst I, and upper strata is catalyst II;Catalyst molecule formula formula is (TiO2)x(SiO2)1-x, wherein
In the molecular formula of catalyst I, x is 0.001~0.08, and in the molecular formula of catalyst II, x is 0.04~0.12.
In order that material can have more preferable mixed effect, and when the lower sides of the reactor arrange 2 groups of injectors, 4
90 degree each other of adjacent 2 injectors in injector.
The present invention also provides a kind of application method that above-mentioned reactor prepares expoxy propane, specifically includes following steps:1)
By isopropyl benzene hydroperoxide and two strands of materials of propylene via 2 injectors in one group of injector spray into respectively reactor lower part,
Head-on collision mixing at a high speed, forms fine particle mixture;2) above-mentioned particles mixture is subsequently entered in the middle part of reactor, and epoxidation occurs
Reaction, generates expoxy propane and dimethyl benzyl alcohol;3) the epoxidation reaction product containing expoxy propane goes out via the gas of reactor
Mouth discharging, by the expoxy propane for isolating and purifying.
Wherein, when the reactor lower part side wall for adopting is provided with 2 groups of injectors, described isopropyl benzene hydroperoxide and third
Two strands of materials of alkene spray into reactor lower part respectively through 2 injectors in any one group of injector.
Described high speed refer to speed that isopropyl benzene hydroperoxide and two strands of materials of propylene spray from injector for 5m/s with
On, preferably 5-30m/s.
Isopropyl benzene hydroperoxide and propylene feed mol ratio 1:1.5~7.0, in order to reduce the use of propylene, reducing energy consumption,
It is preferred that 1:1.5~4.0.
Epoxidation reaction reaction temperature is 40~100 DEG C, and pressure is 2.0~15.0MPa.
In order to prevent exploding, the isopropyl benzene hydroperoxide by injector enter reactor before, first by isopropylbenzene
Hydrogen peroxide is dissolved in formation isopropyl benzene hydroperoxide solution, isopropyl benzene hydroperoxide solution in the solvent for be not involved in epoxidation reaction
The mass concentration of middle isopropyl benzene hydroperoxide is 10%~90%, for the consideration of more security, preferably 15%~45%;Institute
The mixture of the solvent for being not involved in epoxidation reaction that states one kind or two or more arbitrary proportion in alkane, aromatic hydrocarbons and alcohol;
Described alkane preferably is selected from C6~C12Straight or branched alkane, described aromatic hydrocarbons preferably are selected from toluene, ethylbenzene or isopropylbenzene, described
Alcohol preferably is selected from methyl alcohol or isopropanol.
In above-mentioned preparation method, added by injector and in the propylene in reactor, be mixed with propane, propane is mixed at both
In compound, content is 0~16vol%.Propane is generally mixed with industrial propylene, and the content of propane is 0~16vol%, thus
Using industrial propylene cheaper.
The present invention also provides the method that another kind prepares expoxy propane, prepares expoxy propane using reactor assembly, described
Reactor of the reactor assembly described in N+1 claim 1 or 2 be in series, wherein N >=1, the respectively first reaction
Device, second reactor ... ..., N reactors and N+1 reactors, each reactor lower part side wall arrange one group of injector, tool
Production procedure is as follows:
1) propylene is continuously sprayed into first reactor bottom through an injector of first reactor, will be reacted by first
The gaseous phase outlet of device material out is continuously sprayed into second reactor bottom through an injector of second reactor, successively class
Push away other reactors, obtain after isolating and purifying after being most collected by the gaseous phase outlet material out of N+1 reactors at last
Expoxy propane;
2) by isopropyl benzene hydroperoxide through N+1 reactors another injector continuously spray into N+1 reactors under
Portion, the material out of the liquid-phase outlet by N+1 reactors is continuously sprayed into N through another injector of N reactors
Reactor lower part, the like other reactors, be most collected by the liquid-phase outlet material out of first reactor at last;
Wherein, step 1) with step 2) while carry out, through the isopropylbenzene peroxidating that injector sprays into each reactor lower part
, at a high speed after head-on collision mixing, material cocurrent is flowed upwardly in the middle part of reactor, carries out epoxidation reaction, in each reactor for hydrogen and propylene
Gaseous phase outlet material out be the complete propylene of unreacted and epoxidation reaction gas-phase product, through liquid-phase outlet material out
For the complete isopropyl benzene hydroperoxide of unreacted and epoxidation reaction liquid product.
Described high speed refer to speed that isopropyl benzene hydroperoxide and two strands of materials of propylene spray from injector for 5m/s with
On, preferably 5-30m/s.
Isopropyl benzene hydroperoxide and propylene feed mol ratio 1:1.5~7.0, in order to reduce the use of propylene, reducing energy consumption,
It is preferred that 1:1.5~4.0.
Epoxidation reaction reaction temperature is 40~100 DEG C, and pressure is 2.0~15.0MPa.
In order to prevent exploding, the isopropyl benzene hydroperoxide by injector enter reactor before, first by isopropylbenzene
Hydrogen peroxide is dissolved in formation isopropyl benzene hydroperoxide solution, isopropyl benzene hydroperoxide solution in the solvent for be not involved in epoxidation reaction
The mass concentration of middle isopropyl benzene hydroperoxide is 10%~90%, for the consideration of more security, preferably 15%~45%;Institute
The mixture of the solvent for being not involved in epoxidation reaction that states one kind or two or more arbitrary proportion in alkane, aromatic hydrocarbons and alcohol;
Described alkane preferably is selected from C6~C12Straight or branched alkane, described aromatic hydrocarbons preferably are selected from toluene, ethylbenzene or isopropylbenzene, described
Alcohol preferably is selected from methyl alcohol or isopropanol.
In above-mentioned preparation method, be mixed with propane in the propylene in reactor is added by injector, propane is at both
In mixture, content is 0~16vol%.Propane is generally mixed with industrial propylene, and the content of propane is 0~16vol%, because
And using industrial propylene cheaper.
Beneficial effect:
1st, the reactor can realize the head-on collision mixing at a high speed of reactant isopropyl benzene hydroperoxide and propylene, stable so as to be formed
Fine particle mixture, strengthen reaction mass between alternate mixing, strengthen heat and mass effect, reduce side reaction generation,
Isopropyl benzene hydroperoxide conversion ratio and expoxy propane selectivity is improve, cumene hydroperoxide conversion ratio is not less than 87.1%, ring
The selectivity of Ethylene Oxide is not less than 89.6%.
2nd, when the reactor using present invention series connection prepares expoxy propane, cumene hydroperoxide and propylene enter in an inverse manner
Material, both reverse flows between reactor increase storeroom concentration gradient, improve the utilization rate of propylene, reduce the charging of propylene
Amount, reduces the charge ratio of propylene and cumene hydroperoxide, solves turning for improving isopropyl benzene hydroperoxide for prior art presence
Rate, the much excessive problem of propylene.
Description of the drawings
Fig. 1 is structure of reactor schematic diagram;
Fig. 2 is emitter construction schematic diagram;
Fig. 3 is reactor A-A sectional views (1 group of injector);
Fig. 4 is reactor A-A sectional views (2 groups of injectors);
Fig. 5 is the reactor assembly schematic diagram being in series by three reactors, wherein flow direction of the solid line for propylene, dotted line
Flow direction for isopropyl benzene hydroperoxide.
Specific embodiment
For deepening the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and the embodiment is only
For explaining the present invention, limiting the scope of the present invention is not constituted.
Embodiment 1
As shown in Figure 1 and shown in Fig. 3, a kind of reactor, the reactor are fixed bed reactors, are filled with the middle part of reactor
Epoxidation catalyst, roof are provided with gas vent 1, and upper portion side wall is provided with liquid outlet 2, and lower sides are provided with 1 group of spray
Emitter, every group of injector include 2 injectors 3, are distributed in approximately the same plane and mutually symmetrical;As shown in Fig. 2 described injection
The nozzle 6 that device 3 is connected by jet pipe and with jet pipe is constituted, and described nozzle 6 is conical butt, one end that nozzle is connected with jet pipe
With diameter greater than the diameter away from jet pipe one end, nozzle 6 is stretched in fixed bed reactors, and jet pipe is divided into 2 sections, and jet pipe is away from nozzle
One section 7 for cylinder, another section 8 be conical butt, jet pipe is away from nozzle one end with diameter greater than the one end that is connected with nozzle
Diameter.Wherein, the epoxidation catalyst is divided into upper and lower two-layer and is filled in the middle part of reactor, and lower floor is I packed layer of catalyst
4, upper strata is catalyst II packed layer 5, and the molecular formula of described catalyst I is (TiO2)0.001(SiO2)0.009, described catalysis
II molecular formula of agent is (TiO2)0.012(SiO2)0.088.
Embodiment 2
Identical with the structure of embodiment 1, except for the difference that, the molecular formula of catalyst I is (TiO2)0.08(SiO2)0.02, catalysis
II molecular formula of agent is (TiO2)0.04(SiO2)0.06.
Embodiment 3
Identical with the structure of embodiment 1, except for the difference that reactor lower part side wall is provided with 2 groups of injectors, as shown in figure 4,2
90 degree each other of each injector in group injector.
Embodiment 4
The reactor of Application Example 1 prepares expoxy propane, specifically includes following steps:Isopropyl benzene hydroperoxide is dissolved in
Isopropyl benzene hydroperoxide solution is formed in methyl alcohol, the mass concentration of isopropyl benzene hydroperoxide is in isopropyl benzene hydroperoxide solution
24%;Isopropyl benzene hydroperoxide solution is distinguished with 10.1 kg/min of flow with 40.0 kg/min of flow, propylene
Reactor lower part is sprayed into respectively via 2 injectors in one group of injector, in reactor lower part, head-on collision mixes shape at a high speed for both
Nebulize particles mixture, and wherein total propylene is 3.82 with the molar ratio of isopropyl benzene hydroperoxide;Above-mentioned mix particles
Thing is subsequently entered in the middle part of reactor, is 3.5MPa in reaction pressure, under conditions of reaction temperature is 80 DEG C, epoxidation is occurred anti-
Should, generate expoxy propane and dimethyl benzyl alcohol;Epoxidation reaction product containing expoxy propane goes out via the gas vent of reactor
Material, by the expoxy propane for isolating and purifying;After measured, the conversion ratio of isopropyl benzene hydroperoxide is 90.1%, the choosing of expoxy propane
Selecting property is 91.6%.
Embodiment 5
The reactor of Application Example 2 prepares expoxy propane, specifically includes following steps:Isopropyl benzene hydroperoxide is dissolved in
Isopropyl benzene hydroperoxide solution is formed in toluene, the mass concentration of isopropyl benzene hydroperoxide is in isopropyl benzene hydroperoxide solution
21%;In propylene, propane is added to form the gaseous mixture being made up of propane and propylene, propylene mass content is 83% in gaseous mixture;
Isopropyl benzene hydroperoxide solution is sprayed into respectively via an injector in one group of injector with 30.0 kg/min of flow
Reactor lower part, with 8.5 kg/min of flow by the gaseous mixture being made up of propane and propylene via same group of injector in
Another injector sprays into reactor lower part, and isopropyl benzene hydroperoxide solution and the gaseous mixture being made up of propane and propylene are reacting
The at a high speed head-on collision mixing of device bottom, forms vaporific particles mixture, and wherein, total propylene and isopropyl benzene hydroperoxide feed intake mole
Than for 4.0;Above-mentioned particles mixture is subsequently entered in the middle part of reactor, and in reaction pressure 4.8MPa, reaction temperature is 75 DEG C of bar
Under part, there is epoxidation reaction, generate expoxy propane and dimethyl benzyl alcohol;Epoxidation reaction product containing expoxy propane is via anti-
The gas vent of device is answered to discharge, by the expoxy propane for isolating and purifying;After measured, the conversion ratio of isopropyl benzene hydroperoxide is
98.3%, the selectivity of expoxy propane is 95.8%.
Embodiment 6
A kind of preparation method of expoxy propane, prepares expoxy propane, described reaction using reactor assembly as shown in Figure 5
Reactor of the device system described in 3 embodiments 1 is in series, respectively first reactor, second reactor, the 3rd reaction
Device, concrete preparation process are as follows:
1) propylene is continuously sprayed into first anti-through an injector of first reactor with 7.0 kg/min of flow
Answer device bottom, by the material out of the gaseous phase outlet by first reactor through second reactor an injector continuously spray into
Second reactor bottom, the material out of the gaseous phase outlet by second reactor is continuous through an injector of the 3rd reactor
Spray into the 3rd reactor lower part, after the material out of the gaseous phase outlet by the 3rd reactor is collected after isolating and purifying
Obtain expoxy propane;
2) with 40.0 kg/min of flow by isopropyl benzene hydroperoxide solution through the 3rd reactor another injector
Continuously spray into the 3rd reactor lower part, by the material out of the liquid-phase outlet by the 3rd reactor through the another of second reactor
Individual injector is continuously sprayed into second reactor bottom, by by second reactor liquid-phase outlet material out through first reactor
Another injector continuously spray into first reactor bottom, the material by first reactor liquid-phase outlet out is received
Collection;
Wherein, step 1) and step 2) while carrying out, total propylene with the molar ratio of isopropyl benzene hydroperoxide is
1.67;Isopropyl benzene hydroperoxide solution refers to isopropyl benzene hydroperoxide is dissolved in hexane and is formed, isopropyl benzene hydroperoxide
In solution, the mass concentration of isopropyl benzene hydroperoxide is 38%;
After spraying into the isopropyl benzene hydroperoxide solution and propylene head-on collision mixing of each reactor lower part through injector, material is simultaneously
Stream is flowed upwardly in the middle part of reactor, in reaction pressure 4.8MPa, under conditions of reaction temperature is 80 DEG C, carries out epoxidation reaction,
It is the complete propylene of unreacted and epoxidation reaction gas-phase product through the gaseous phase outlet material out of each reactor, liquid-phase outlet
Material out is the complete isopropyl benzene hydroperoxide of unreacted and epoxidation reaction liquid product;After measured, isopropylbenzene peroxidating
The conversion ratio of hydrogen is 95.4%, and the selectivity of expoxy propane is 95.9%.
Embodiment 7
A kind of preparation method of expoxy propane, prepares expoxy propane, described reaction using reactor assembly as shown in Figure 5
Reactor of the device system described in 3 embodiments 1 is in series, respectively first reactor, and second reactor and the 3rd is reacted
Device, concrete preparation process are as follows:
1) with 8.0 kg/min of flow by the gaseous mixture being made up of propane and propylene via one of first reactor
Injector is continuously sprayed into first reactor bottom, by the material out of the gaseous phase outlet by first reactor through second reactor
An injector continuously spray into second reactor bottom, will be anti-through the 3rd for the material by second reactor gaseous phase outlet out
One injector of device is answered continuously to spray into the 3rd reactor lower part, by the material collection out of the gaseous phase outlet by the 3rd reactor
By obtaining expoxy propane after isolating and purifying;
2) with 30.0 kg/min of flow by isopropyl benzene hydroperoxide solution through the 3rd reactor another injector
Continuously spray into the 3rd reactor lower part, by the material out of the liquid-phase outlet by the 3rd reactor through the another of second reactor
Individual injector is continuously sprayed into second reactor bottom, by the material out of the liquid-phase outlet by second reactor through the first reaction
Another injector of device is continuously sprayed into first reactor bottom, and the material out of the liquid-phase outlet by first reactor is entered
Row is collected;
Wherein, step 1) and step 2) while carrying out, total propylene with the molar ratio of isopropyl benzene hydroperoxide is
1.95, in the gaseous mixture being made up of propane and propylene, propylene mass content is 83%;Isopropyl benzene hydroperoxide solution is referred to will be different
Cumene hydroperoxide is dissolved in isopropanol and is formed, and in isopropyl benzene hydroperoxide solution, the mass concentration of isopropyl benzene hydroperoxide is
41%;
The isopropyl benzene hydroperoxide solution of each reactor lower part is sprayed into and by mixing that propylene and propane are constituted through injector
After closing gas head-on collision mixing, material cocurrent is flowed upwardly in the middle part of reactor, is 3.3MPa in reaction pressure, and reaction temperature is 75 DEG C
Under the conditions of, epoxidation reaction is carried out, is the complete propylene of unreacted and epoxy through the gaseous phase outlet material out of each reactor
Change reaction gas-phase product, liquid-phase outlet material out is that the complete isopropyl benzene hydroperoxide of unreacted and epoxidation reaction liquid phase are produced
Thing;After measured, the conversion ratio of isopropyl benzene hydroperoxide is 99.2%, and the selectivity of expoxy propane is 97.2%.
Embodiment 8
A kind of preparation method of expoxy propane, prepares expoxy propane, described reaction using reactor assembly as shown in Figure 5
Reactor of the device system described in 3 embodiments 2 is in series, respectively first reactor, and second reactor and the 3rd is reacted
Device, concrete preparation process are as follows:
1) gaseous mixture being made up of propane and propylene is sprayed for one through first reactor with 16.9 kg/min of flow
Device is continuously sprayed into first reactor bottom, by the material out of the gaseous phase outlet by first reactor through the one of second reactor
Individual injector is continuously sprayed into second reactor bottom, by the material out of the gaseous phase outlet by second reactor through the 3rd reaction
One injector of device is continuously sprayed into the 3rd reactor lower part, after by the 3rd reactor gaseous phase outlet material collection out
Separated obtain expoxy propane after purification;
2) with 50.0 kg/min of flow by isopropyl benzene hydroperoxide solution through the 3rd reactor another injector
Continuously spray into the 3rd reactor lower part, by the material out of the liquid-phase outlet by the 3rd reactor through the another of second reactor
Individual injector is continuously sprayed into second reactor bottom, by by second reactor liquid-phase outlet material out through first reactor
Another injector continuously spray into first reactor bottom, the material by first reactor liquid-phase outlet out is carried out
Collect;
Wherein, step 1) and step 2) while carrying out, total propylene with the molar ratio of isopropyl benzene hydroperoxide is
3.77, in the gaseous mixture being made up of propane and propylene, propylene mass content is 80%;Isopropyl benzene hydroperoxide solution is referred to will be different
Cumene hydroperoxide is dissolved in isopropanol and is formed, the mass concentration of isopropyl benzene hydroperoxide in isopropyl benzene hydroperoxide solution
26%;
The isopropyl benzene hydroperoxide solution of each reactor lower part is sprayed into and by mixing that propylene and propane are constituted through injector
After closing gas head-on collision mixing, material cocurrent is flowed upwardly in the middle part of reactor, and in reaction pressure 2.5MPa, reaction temperature is 90 DEG C of bar
Under part, epoxidation reaction is carried out, be the complete propylene of unreacted and epoxidation through the gaseous phase outlet material out of each reactor
Reaction gas-phase product, liquid-phase outlet material out are that the complete isopropyl benzene hydroperoxide of unreacted and epoxidation reaction liquid phase are produced
Thing;After measured, the conversion ratio of isopropyl benzene hydroperoxide is 99.5%, and the selectivity of expoxy propane is 98.2%.
Presently preferred embodiments of the present invention is the foregoing is only, not in order to limit the present invention, all in essence of the invention
Within god and principle, any modification, equivalent substitution and improvements that is made etc. should be included in protection scope of the present invention.