CN107855078A - One kind is used for alkene and the epoxidised isothermal adiabatic reactor of hydroperoxides - Google Patents
One kind is used for alkene and the epoxidised isothermal adiabatic reactor of hydroperoxides Download PDFInfo
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- CN107855078A CN107855078A CN201711372688.6A CN201711372688A CN107855078A CN 107855078 A CN107855078 A CN 107855078A CN 201711372688 A CN201711372688 A CN 201711372688A CN 107855078 A CN107855078 A CN 107855078A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
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- 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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
Abstract
The present invention relates to one kind to be used for alkene and the epoxidised isothermal adiabatic reactor of hydroperoxides, epoxidation reaction especially suitable for propylene and hydroperoxides, it includes upper and lower end socket, isothermal catalyst reaction section and the upper tube box and lower tube box for being located at isothermal catalyst reaction section both ends, the adiabatic catalytic conversion zone being located between upper tube box and upper cover；The adiabatic catalytic conversion zone includes adiabatic piece housing, the catalyst pressing plate being fixedly connected with adiabatic piece housing and supporting plate, and adiabatic section catalytic bed is provided between the catalyst pressing plate and supporting plate.The present invention can significantly simplify traditional reaction process, and device therefor is few, reduce process complexity, while temperature is easily controllable, and catalyst life length, hydroperoxides can react completely in this equipment.
Description
Technical field
The invention belongs to chemical reactor technology field, and in particular to one kind is used for alkene and hydroperoxides epoxy
The isothermal adiabatic reactor of change, the epoxidation reaction especially suitable for propylene and hydroperoxides.
Background technology
Expoxy propane is one of important intermediate of petrochemical industry.In propylene derived product, expoxy propane is currently only
Inferior to polypropylene and the third-largest derivative of acrylonitrile.Expoxy propane is industrially mainly for the preparation of PPG, and the third two
Alcohol, hydramine and all kinds of nonionic surfactants, its derivative are widely used in petrochemical industry, building, household electrical appliances, automobile, medicine, agriculture
The industries such as medicine, weaving, daily use chemicals.
Traditional propylene oxide production process is chlorohydrination, and feature is that process CIMS is short, technical maturity, operational load elasticity
Larger, good, the high income of selectivity, comparision of production safety, not high to raw material propylene purity requirement, construction investment is few；But chlorohydrination
The waste water of a large amount of chloride containing calcium can be produced during production expoxy propane, environment is caused seriously to pollute.Thus, each state is all in product
The economic green Producing Process of Propylene Oxide of pole exploitation cleaning.
Current non-propylene oxide by chlorohydrination production line can be divided into conjugated oxidation, peroxide passivation, the class of direct oxidation method three.
Conjugated oxidation can be divided into ethylbenzene method, iso-butane method, cumene method etc. again by the different of organic matter hydrogen peroxide, and this kind of method is mesh
Former world is just with widest expoxy propane Green Manufacturing Technology；Peroxide passivation is using hydrogen peroxide and propylene oxidation generation ring
The technology of Ethylene Oxide, the techniqueflow is simple, effect on environment is small, studies at home more；And the direct oxidation method of propylene is
The most economical production method of atom, but the experimental study stage is remained at present, not yet find suitable catalysis material.
Alkene conjugated oxidation technique is earliest by Halcon companies（It is now Lyondell companies）In 1967 in US
Delivered in 3351635.The cooxidation of alkene and organic hydroperoxide is reacted typically at 50 ~ 120 DEG C, is entered under the conditions of 1000psi
OK, in order to propylene is reacted under liquid-phase condition.
Specific to expoxy propane, its course of reaction is：
R-OOH + CH3CH=CH2 ――→ R-OH + CH3CHOCH2
Wherein R is organic group, can be ethylbenzene, cumenyl, the tert-butyl group, isopentyl, cyclopenta, cyclohexyl etc..
At present, industrialized cooxidation propylene oxide process have epoxypropane-vinyl benzene joint production process, expoxy propane-
The tert-butyl alcohol（Or methyl tertiary butyl ether(MTBE)）Joint production process, cumene method propylene oxide process.
The joint production process of expoxy propane and styrene mainly includes ethylbenzene liquid phase oxidation generation ethylbenzene hydroperoxide, ethylbenzene mistake
Hydrogen oxide and propylene liquid phase cooxidation generation 1- benzyl carbinols and expoxy propane, dehydration generation three reactions of styrene of 1- benzyl carbinols,
The specific patent US5210354 described referring to ARCO companies.The joint production process of expoxy propane and the tert-butyl alcohol mainly includes isobutyl
Alkane liquid phase oxidation generates TBHP, TBHP and the propylene liquid phase cooxidation generation tert-butyl alcohol and epoxy third
Alkane, the tert-butyl alcohol can also be further converted to methyl tertiary butyl ether(MTBE)（MTBE）, the specific patent described referring to ARCO companies
US5424458.Cumene method propylene oxide process and epoxypropane-vinyl benzene joint production process and expoxy propane-tert-butyl alcohol（Or first
Base tertbutyl ether）The main difference of joint production process is that joint product dimethyl benzyl alcohol is hydrogenated into the circulation of raw material isopropylbenzene makes
With, and the liquid phase cooxidation technique of the liquid phase oxidation of isopropylbenzene, isopropyl benzene hydroperoxide and propylene and the cooxidation of ARCO companies
Technique is similar, the specific patent CN1856482 described referring to Sumitomo Chemical.
In the patent US3351635 of Halcon companies, the cooxidation for describing alkene and organic peroxide reacted
Journey：Propylene and organic hydroperoxide carry out liquid phase epoxidation reaction under the conditions of preferred 50-120 DEG C, 1000psi.In epoxidation
During, the molybdenum that can be dissolved in reaction mass, tungsten, titanium, niobium, tantalum, rhenium, selenium, chromium, zirconium, tellurium, uranium series homogeneous catalysis can be used
Agent.
The reaction of propylene cooxidation also has the work using heterogeneous catalysis in addition to using homogeneous catalyst as described above
Skill.The process of alkene epoxidation is described in the patent US8664412 of Shell companies, the difference with Halcon techniques is to adopt
With heterogeneous solid-phase epoxy catalyst.Shell companies describe one kind in its patent US3829392 and are used for alkene ring
The TiO2 of oxidation is carried on the solid-phase catalyst on SiO2.In addition to the TiO2-SiO2 type catalyst of Shell companies, Japan lives
The cumene method technique of friendly chemistry also carries out epoxidation reaction using solid-phase catalyst.Sumitomo Chemical is in patent CN1953969
A kind of preparation method of expoxy propane is described, one kind is employed and is more easy to produce, the lower titan silicate solid-phase catalyst of cost.
Except conjugated oxidation, peroxide passivation propylene oxide process is then directly using hydrogen peroxide and propylene reaction generation epoxy
Propane.Peroxide passivation at present（HPPO methods）Expoxy propane has been industrialized by BASF AG（BASF）And DOW Chemical
（Dow）The technology of joint development and by Ying Chuan groups（Former Degussa, Degussa）With Wood company（Uhde）Joint development
Technology.The difference of two kinds of technologies is mainly the type of reactor of epoxidation reaction, and the two is all in catalysis technique particularly titanium silicon
Gradually moved to maturity under its development of molecular sieve TS-1.（Liu Bo, Zhang Xiaoli, Zhao Li, wait production of propylene oxide works
Current situation [J] present age chemical industry of skill, 2016,45 (2): 336- 341）.
Compared with Halcon method propylene oxide process, Shell methods propylene oxide process, Sumitomo method propylene oxide process and mesh
Preceding peroxide passivation propylene oxide process employs solid-phase epoxy catalyst.Compared with homogeneous epoxidation technique, due to adopting
With solid phase cooxidation catalyst, the separating step of catalyst and material is eliminated, simplifies reaction process, simultaneously because reaction
Residence time is few, and reaction back-mixing is few, thus side reaction is few, and consumption of raw materials is small, and product separation is also relatively easy.Thus, in order to carry
The selectivity of high cooxidation reacting epoxy propane, it is more advantageous using solid-phase catalyst.
The solid-phase catalyst for being presently used for cooxidation is using TiO2 as the active SiO2 type catalyst formed, state substantially
This type is being studied by interior such as Shanghai Petroleum Chemical Engineering Institute (CN1268400), Dalian University of Technology (CN103464197A)
Catalyst.
Either Halcon techniques, or shell techniques, it is third in epoxidation reaction also or hydrogen peroxide process
Alkene and organic hydroperoxide（Or hydrogen peroxide）Reacted.And the heat endurance of peroxide is poor, during the course of the reaction can
Decompose, and temperature is higher, decomposition rate is faster.Such as SUMITOMO CHEMICAL chemistry described in its patent CN01806929 it is different
The decomposition situation of cumene hydroperoxide.Isopropyl benzene hydroperoxide has a suitable temperature in use, can be expressed with following formula：
t = 150-0.8*w
Wherein, t is the permission temperature in use of isopropylbenzene hydroperoxide material, DEG C；W is isopropyl benzene hydroperoxide in material
Mass content, %.
The isopropylbenzene hydroperoxide logistics of same concentration, in operation temperature T<It is different when 30min is operated under conditions of t
Cumene hydroperoxide resolution ratio is 2 ~ 3%, and in operation temperature T>When 30min is operated under conditions of t, isopropyl benzene hydroperoxide
Resolution ratio then up to 20 ~ 25%.
With the rise of temperature, the thermal decomposition rate of isopropyl benzene hydroperoxide is accelerated, meanwhile, with isopropyl benzene hydroperoxide
Concentration increase in material, the notable decomposition temperature point of isopropyl benzene hydroperoxide can also reduce, and this phenomenon is not only isopropyl
Benzene hydrogen peroxide property, having with ethylbenzene hydroperoxide, TBHP, hydrogen peroxide etc. during oxide also has this existing
As.
In cooxidation reaction, in order to improve the selectivity of expoxy propane, it is necessary to reduce the decomposition of organic hydroperoxide.Wherein
It is one of them far-reaching factor to reduce thermal decomposition（In addition to thermal decomposition, organic hydroperoxide is also easy to that sour decomposition occurs
With caustic digestion-Cao Gang cumene methods production phenol-acetone [M] Chemical Industry Press, 1983.）.Organic hydroperoxide
（Hydrogen peroxide）When decomposing the corresponding alcohol of generation, ketone, while elemental oxygen can be lost：R-OOH → R-OH + [O]
The presence of elemental oxygen can cause the over oxidation of organic matter, increase the acid content in reaction system, and this can promote to have again
The acid decomposition of machine hydrogen peroxide, meanwhile, organic acid is a kind of alkylation catalyst in itself, and can cause the polymerization of alkene, and this is all
Undesirable side reaction increase can be caused.
Thus, in order to improve the selectivity of expoxy propane, operation is favourable at low temperature for cooxidation reaction.Such as Halcon
The alkene of technique and the cooxidation preferable temperature of organic peroxide are 50-120 DEG C（US3351635）.
Because cooxidation reaction is exothermic reaction, reaction heat can be released when cooxidation reacts and carried out, causes reaction temperature
Continuous improvement, this can cause the increase of side reaction again, or even cause the uncontrollable decomposition of organic hydroperoxide.
In order to solve this problem, cooxidation can be reacted segmentation and carried out, the conversion of every section of control organic hydroperoxide
Rate, it is unlikely too high with the outlet temperature of control reaction, cooled down again between every section, to ensure the temperature of whole cooxidation reaction
Spend controllable.As ARCO companies patent CN 1688562A in using at least two series connection fixed bed reactors, alkene and hydrogen mistake
After oxide enters the two reactor reactions, another is entered back into equipped with the anti-of at least partly epoxidation catalyst of inactivation
Answer device.The cooxidation structure of reactor of Shell companies is increasingly complex（Such as CN00811661.X, CN02809522.7）It is general shared
6 cooxidation adiabatic reactors, 5 drivings during normal use, 1 regeneration（Open acryloyl derivatives engineering [M] chemistry of the rising sun
Industrial publishing house, 1995.）.
The epoxidation for similarly employing the also sinopec that multistage insulation fixed bed reactor carries out epoxidation reaction is anti-
Answer technology, such as CN201310512322.X, CN201310683291.4, CN201410353282.3, CN201410353238.2.
Make again although the application of heterogeneous cooxidation catalyst improves the selectivity of expoxy propane, the problem of reaction temperature rising
The selectivity of expoxy propane declines, and epoxidation reaction is split into multistage can cause the complication of equipment, and this is solid at present
The subject matter of fixed bed epoxidation reactor.In addition, during using fixed bed reactors, inlet temperature is relatively low, and outlet temperature compared with
Height, do not ensure that cooxidation reaction is carried out at optimum temperature, this had both been caused under the catalyst utilization of low-temperature space
Drop, it also result in the reduction of high-temperature region expoxy propane selectivity.
In cooxidation reaction, in addition to considering to improve the selectivity of expoxy propane, the complete conversion of organic hydroperoxide
It is very important.Because the temperature of cooxidation piece-rate system is typically more much higher than cooxidation reactor, organic hydrogen peroxide
After compound brings piece-rate system into, can uncontrollably it be thermally decomposed, this can cause the increasing of alkylation and olefinic polymerization side reaction
Add, meanwhile, the elemental oxygen for thermally decomposing releasing will also result in the security risk dived, but be difficult to predict specific location at risk.
In addition, organic peroxide has deactivation to microorganism, into waste water after can not be handled with activated sludge process.Thus,
Organic hydroperoxide must be converted completely in cooxidation reactor.In order to reach the mesh that organic hydroperoxide converts completely
, ARCO is post-processed using a single reactor to cooxidation discharging（CN 1688562A）, but cause cooxidation
The complication of reaction system.
Although the patent of ARCO companies and the device of Shell companies both provide the alkene and hydroperoxides ring on basis
The flow and consersion unit of oxidation, but flow is excessively complicated, and the occupation of land of reactor group is larger, and reaction temperature changes greatly, epoxy
The selectivity of propane is low, and this also result in the increase of equipment investment and the loss of reaction mass.
The content of the invention
Take up an area that larger, temperature, which is difficult to control, hydroperoxides can not react completely asks for existing epoxidation reactor
Topic, the present invention provide one kind and are used for alkene and the epoxidised isothermal adiabatic reactor of hydroperoxides, and its temperature is easily controllable, hydrogen
Peroxide can react completely in this equipment.
To achieve these goals, the technical scheme is that：
One kind is used for alkene and the epoxidised isothermal adiabatic reactor of hydroperoxides, including upper and lower end socket, isothermal catalytic reaction
Section and the upper tube box and lower tube box for being located at isothermal catalyst reaction section both ends, the adiabatic catalytic being located between upper tube box and upper cover are anti-
Answer section；The adiabatic catalytic conversion zone includes adiabatic piece housing, the catalyst pressing plate being fixedly connected with adiabatic piece housing and support
Plate, adiabatic section catalytic bed is provided between the catalyst pressing plate and supporting plate.
The present invention uses two-stage catalytic reaction bed structure, and isothermal catalyst reaction section is used to improve target product epoxy third
The selectivity of alkane, benzyl carbinol and acetophenone；And adiabatic catalytic conversion zone is used to ensure that the conversion ratio of hydroperoxides is more than
99.9%, or conversion completely.The present invention is especially suitable for the alkene of middle and small scale and hydroperoxides coproduction to react.
As a further improvement on the present invention：The isothermal catalyst reaction section includes tube side and shell side, is passed in the shell side
Thermal medium import and export is correspondingly provided with circle distributor respectively, and the annular sidewall of the circle distributor is to be provided with multiple apertures
Porous plate or strip-type grille.
As a further improvement on the present invention：Perforated area on the porous plate or strip-type grille is from circle distributor
Import gradually linearly reduced to distributor end, so as to reach being uniformly distributed for shell-side heat catalysis, so as to ensure that tube side
The isothermal of interior catalytic reaction bed temperature, the temperature difference are no more than 6 degree.
The beneficial effects of the present invention are：
1st, the present invention uses two-part catalytic bed structure, and the isothermal catalyst reaction section of hypomere can withdraw reaction heat in time, reduces
The decomposition of hydroperoxides, the selectivity of target product is improved, and the adiabatic catalytic conversion zone of epimere can be not complete by isothermal bed
The conversion completely of the hydroperoxides of full response is fallen, and reduces the loss of material in last handling process.
2nd, the present invention changes the traditional structure of original circle distributor, devises the annular spread of new gradual change type structure
Device so that temperature, the inlet and outlet temperature difference of pipe are maintained within 6 degree between pipe, anti-so as to ensure and realize isothermal section
That answers bed waits temp effect.
3rd, can be carried out because present invention employs isothermal section reaction bed, epoxidation reaction in one section of reaction bed,
This can significantly simplify traditional reaction process, and auxiliary device is also few, and its separate unit reactor is alternative more reactor systems of tradition
System, also reduces equipment investment while reducing process complexity.
4th, quickly to be withdrawn because present invention employs the reaction heat energy of isothermal section reaction bed, epoxidation reaction, this meaning
The operation temperature that taste catalytic bed can be always held at a relatively low optimal temperature, substantially increase making for catalyst
With life-span and overall utilization rate, the complete conversion ratio of hydroperoxides is improved.So as to overcome traditional adiabatic reactor defect：
Due to outlet temperature to be limited in one it is relatively low, hydroperoxides decompose controllable temperature, thus must limiting inlet material
In relatively low temperature, and the reaction rate of feeding part can be so reduced, which results in the reactor of adiabatic section, at charging
Catalyst utilization deficiency, and in discharging, catalyst operates at high temperature for a long time, and load is again too big, has both caused the wave of catalyst
Take, also reduce the overall utilization rate of catalyst, while be also easy to cause the incomplete conversion of hydroperoxides.
5th, the present invention devises adiabatic catalytic conversion zone after isothermal section reaction bed, it is ensured that by the complete of hydroperoxides
Full conversion, it is easy to improve the yield of target product expoxy propane, benzyl carbinol and acetophenone.So as to overcome existing equipment due to hydrogen
When peroxide does not convert completely, after-treatment system can be entered with reaction mass, and in after-treatment system, hydrogen peroxide
Compound can follow thermal decomposition or sour decomposition mechanism is decomposed, and caused elemental oxygen easily causes the olefinic polymerization in reaction product
The defects of.
Brief description of the drawings
Fig. 1 is the structure of reactor schematic diagram of invention；
Fig. 2 is the tubulation and Heating medium structure of distributor schematic diagram of isothermal catalyst reaction section of the present invention；
Fig. 3 is the A-A schematic diagrames of circle distributor in this Fig. 2；
In accompanying drawing：1 is housing, and 2 be upper cover, and 3 be low head, and 4 be liquid outlet, and 5 be adiabatic piece housing, and 6 be catalyst pressing plate,
7 be adiabatic section catalytic bed, and 8 be supporting plate, and 9 be upper tube box；10 be upper perforated plate, and 11 be heating agent outlet distributor, and 12 be tubulation,
13 be deflection plate, and 14 be Heating medium distributor, and 141 be Heating medium distributor import, and 15 be lower tube box, and 16 be lower perforated plate,
17 be inlet, and 18 be annular sidewall, and 19 be aperture.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.
Embodiment 1：
As shown in Figure 1-Figure 3, the alkene of the present invention that is used for includes with the epoxidised isothermal adiabatic reactor of hydroperoxides：Band
There are the cylindrical housings 1 of upper cover 2 and low head 3, the top of upper cover 2 is provided with reaction product liquid outlet 4；The cylindrical housings
1 point is upper and lower two sections；Epimere is adiabatic catalytic conversion zone, and it is by adiabatic piece housing 5, catalyst pressing plate 6, adiabatic section catalytic bed
Layer 7 and supporting plate 8 are formed；Hypomere is isothermal catalyst reaction section, and isothermal catalyst reaction section both ends are respectively equipped with the He of upper tube box 9
Lower tube box 15；The bottom of low head 3 is provided with reaction raw materials inlet 17.
As depicted in figs. 1 and 2：Isothermal catalyst reaction section is divided into tube side and shell side, and tube side is made up of more tubulations 12, upper tube
Upper perforated plate 10, lower perforated plate 16 are respectively equipped with case 9 and lower tube box 15, the more tubulations 12 are arranged on upper perforated plate 10, lower perforated plate
Between 16, tubulation 12 is used to load catalyst, and it is heating agent that pipe is outer, with controlling reaction temperature.It is in order that warm in each reaction tube 12
Degree is uniform, and the shell side that thermal medium enters outside reaction tube sets Heating medium distributor 14, and there is provided heating agent outlet for shell-side outlet
Distributor 11, Heating medium distributor 14 and heating agent outlet distributor 11 are all circle distributors, in order to ensure flow rate of heat medium
It is circumferentially distributed uniformly, the annular sidewall 18 of circle distributor is the porous plate or strip-type grille for opening up multiple apertures 19, this reality
It is to set the porous plate of multiple apertures 19 to apply example, as shown in figure 3, the perforated area of Heating medium distributor 14 is from distributor import
Gradually linearly reduced to distributor end at 141, the perforated area of same heating agent outlet distributor 11 is at sparger outlets
Gradually linearly reduced to distributor end, constantly rise convection body distribution so as to adapt to heating agent pressure in import circular passage
Influence, adapt to heating agent pressure in circular passage export and constantly decline the influence that convection body is distributed, it is ensured that heating agent is along isothermal section
Reactor circumferencial direction is evenly distributed.Shell side is provided with deflection plate 13, and the form of deflection plate 13 is disc.
The operation principle of reactor of the present invention is：Heating agent enter from the aperture of import distributor between tubulation and in tubulation it is anti-
Material-heat-exchanging is answered, is flowed at backward reactor axle center；Thereafter it is first upward at axle center, after outwards flowed along deflection plate, flow through more
Outside is reached after root tubulation and reaction mass heat exchange, the excessive root tubulation that then flows over again flows at reactor axle center, so
It is repeated multiple times, enter outlet circuit finally by the aperture of heating agent outlet distributor, then export and flow out from heating agent.
Reaction mass enters reactor lower tube box from inlet after import distributor, subsequently into reaction tube with
Catalyst contacts, and epoxidation reaction occurs in the presence of catalyst, is flowed out after reaction from reaction tube upper end, by upper tube box
Into adiabatic catalytic conversion zone, further reacted herein with epoxidation catalyst, because adiabatic catalytic conversion zone is not removed instead
Should be hot, reaction liberated heat will cause reaction mass itself adiabatic heating, ensure that and be reacted in higher temperature,
Although the selectivity of reaction has declined, but ensure that reaction is compared thoroughly.The reaction that adiabatic catalytic conversion zone is formed
Material is from upper cover liquid outlet outflow reactor.
By implementing above technical measures, it can be ensured that reach goal of the invention：Reaction pressure is 2.0-10.0MPa, temperature
50-120 DEG C, residence time 0.2-2hr-1, conversion ratio >=80% of hydroperoxides, preferably>90%, more preferably>95%, epoxy
Propane selectivity can reach 98-99%；Enter adiabatic section beds from the material of isothermal section outflow, make hydroperoxides
Conversion ratio is more than 99.9%, or conversion completely.
80,000 tons/year of expoxy propane -20, ten thousand tons of styrene coproduction reactions are used for using above-described embodiment structural response device：This
The structural dimensions data of invention reactor, are shown in Table 1.
Table 1
| Project | Size, mm |
| Diameter | 5400 |
| Total height (cylinder) | 18700 |
| Tubulation height | 12000 |
| Tubulation diameter | 57 |
| Tubulation quantity | 3966 |
| Adiabatic catalytic conversion zone height | 1100 |
Reactor of the present invention is respectively used to 80,000 tons/year of expoxy propane -20, ten thousand tons of styrene coproduction fashionable dresses with con-ventional insulation reactor
The contrast table put, is shown in Table 2.
Table 2
| Project | Traditional reactor | Reactor of the present invention |
| Type of reactor | It is adiabatic | |
| Reactor number of units | 5 ~ 6 | 1 ~ 2 |
| Reaction temperature controllability | Inlet temperature can only be controlled | Import and export temperature is controllable |
| Catalyst life | ~ March | More than June |
| Alcohol ketone selectivity, % | ~98 | 98~99 |
| Hydroperoxide conversion, % | 99 | 99.9 |
It can be seen that the present invention can significantly simplify traditional reaction process, device therefor is few, reduces process complexity, is catalyzed simultaneously
Agent long lifespan.
Embodiment 2
Using reactor of the present invention, structural dimensions data are：Internal diameter is 50mm, and isothermal catalyst reaction section is highly 1m, absolutely
Heat catalysis section is highly 0.2m, using upper TiO2It is carried on SiO2The catalyst of carrier, propylene and ethylbenzene peroxidating are carried out
The experiment of hydrogen (EBHP), experiment condition such as table 3；Experimental result such as table 4.
Table 3
| Experiment condition | Index |
| Reaction temperature, DEG C | 80 |
| Reaction pressure, MPaG | 4.5 |
| Propylene/EBHP, mol/mol | 6 |
| EBHP weight (hourly) space velocity (WHSV)s, h-1 | 0.8 |
Table 4
| Assessment item | Evaluation result |
| EBHP isothermal section conversion ratios % | 95% |
| EBHP conversion ratios, % | 100% |
| Alcohol ketone selectivity, % | ~99% |
It should be appreciated that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not intended to limit the invention, it is all in the present invention
Spirit and principle within all any modification, equivalent and improvement made etc., should be included in protection scope of the present invention it
It is interior.
Claims (3)
1. one kind is used for alkene and the epoxidised isothermal adiabatic reactor of hydroperoxides, it is characterised by：Including upper and lower end socket,
Isothermal catalyst reaction section and the upper tube box and lower tube box for being located at isothermal catalyst reaction section both ends, are located between upper tube box and upper cover
Adiabatic catalytic conversion zone；The catalysis that the adiabatic catalytic conversion zone includes adiabatic piece housing, is fixedly connected with adiabatic piece housing
Agent pressing plate and supporting plate, adiabatic section catalytic bed is provided between the catalyst pressing plate and supporting plate.
2. isothermal adiabatic reactor according to claim 1, it is characterised in that：The isothermal catalyst reaction section includes tube side
And shell side, heat catalysis import and export is correspondingly provided with circle distributor, the annular side of the circle distributor respectively in the shell side
Wall is the porous plate or strip-type grille for being provided with multiple apertures.
3. isothermal adiabatic reactor according to claim 2, it is characterised in that：On the porous plate or strip-type grille
Perforated area is gradually linearly reduced from the import of circle distributor to distributor end.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711372688.6A CN107855078A (en) | 2017-12-19 | 2017-12-19 | One kind is used for alkene and the epoxidised isothermal adiabatic reactor of hydroperoxides |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711372688.6A CN107855078A (en) | 2017-12-19 | 2017-12-19 | One kind is used for alkene and the epoxidised isothermal adiabatic reactor of hydroperoxides |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110787739A (en) * | 2018-08-03 | 2020-02-14 | 中国石化工程建设有限公司 | Device and method for generating epoxyalkane by reacting alkylbenzene peroxide with low-carbon olefin |
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