CN107879899A - A kind of apparatus and method of the continuous isomerization of epoxides - Google Patents
A kind of apparatus and method of the continuous isomerization of epoxides Download PDFInfo
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- CN107879899A CN107879899A CN201711218603.9A CN201711218603A CN107879899A CN 107879899 A CN107879899 A CN 107879899A CN 201711218603 A CN201711218603 A CN 201711218603A CN 107879899 A CN107879899 A CN 107879899A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to a kind of apparatus and method of the continuous isomerization of epoxides, and corresponding allyl alcohol product is prepared available for the continuous isomerization of epoxides.Methods described includes reaction raw materials and carrier gas being preheated to certain temperature, raw material is contacted with the regenerated catalyst and new supplement catalyst for entering fluidized-bed reactor and fluidized state according to certain air speed, isomerization reaction is carried out under pressure, isolated reaction gas and carbon deposition catalyst in settler, wherein, reaction gas rises enters product separation system through reaction solution pipeline at the top of settler, carbon deposition catalyst regenerates into regenerator, and catalyst line returns to riser reactor to the catalyst after regeneration after regeneration.The technique has high Atom economy, product yield and selectivity height, the free of contamination feature of technique, hence it is evident that better than current slurry bed process.
Description
Technical field
The present invention relates to a kind of Circulating Fluidized Bed Process and in continuous isomerization application, specifically a kind of epoxides
The apparatus and method of continuous isomerization, corresponding allyl alcohol product is prepared available for the continuous isomerization of epoxides.
Background technology
Allyl alcohol is a kind of important chemical intermediate and fine chemical product, due to containing double bond and hydroxyl in molecular structure
Ji Liangzhong functional groups, oxidation, reduction, esterification, etherificate and addition etc. are may participate in, in chemicals, medicine, spices and organic synthesis
Etc. tool have been widely used.Main derivative and application thereof is：For synthesizing epoxy chloropropane, glycerine, Isosorbide-5-Nitrae-fourth two
The important organic synthesis raw material such as alcohol and allyl ketone, its important derivatives allyl ester mainly as production polymer monomer or
Performed polymer.
Allyl alcohol synthesis before this mainly can so be produced using the method synthesis of allyl chloride hydrolysis, allyl chloride hydrolysis process
Containing a large amount of chloride wastewaters, waste liquid.The current production technology of allyl alcohol produces a large amount of waste water, waste liquid, with people to environmental protection and
Chemical reaction Atom economy requirement gradually step up, developing low-cost, in high yield, the production process of low stain turn into future
The inexorable trend of development of chemical industry, therefore there is an urgent need to a kind of scheme of more green high-efficient.
Epoxides isomerization, which prepares corresponding allyl alcohol, has that technique is simple, high income, corrosion-free to equipment, without " three
It is useless " pollute the advantages that producing.At present, it is lithium phosphate to react maximally efficient catalyst as catalysis propylene oxide isomerization, institute
So that it has also obtained extensive commercial Application at present.Epoxides isomerization prepares corresponding allyl alcohol two methods again, point
Wei not vapor phase method and slurry reaction method.Vapor phase method uses tabletting or extruded moulding catalyst, and fixed bed is as reactor, due to different
Structure process can generate a large amount of reactive intermediates, and polymerization, which easily occurs, causes catalyst carbon deposition, and catalyst life is shorter.United States Patent (USP)
US4720598 discloses a kind of vapor phase method synthesis and regeneration technology, and 255-260 DEG C of reaction temperature, expoxy propane is urged in lithium phosphate
The lower isomery generation allyl alcohol of agent catalysis, vapor phase method use fixed bed reactors, with flow is short, the spy of allyl alcohol high income
Point, but catalyst inactivation is exceedingly fast, and catalyst uses 30h, and loss of activity reaches 50%.Frequent switching is needed to regenerate, production efficiency
It is low, it is unsatisfactory for industrialization production requirements.United States Patent (USP) US3238264 discloses the method that slurry method prepares allyl alcohol, its feature
It is, using powder lithium phosphate catalyst, catalyst to be suspended in high boiling solvent and reacted, needs constantly to take out in course of reaction
Go out the decaying catalyst that simultaneously separate section suspends, to isolate the tar being attached on oil reservoir, it possesses catalyst and is continuously added to,
The characteristics of continuous extraction, but due to using a large amount of high boiling solvents, solvent loss be present, and due to the presence of high boiler, lead
Gas-liquid-solid diffusion is caused to turn into rate constants, reactivity is decreased obviously, and causes reaction time to be grown, side reaction is more.
Fluidized-bed reactor has gas solid transfer efficiency high, and reaction rate is fast, the advantages of solvent-free loss, due to catalyst
The reason for intensity etc., still it is not applied in epoxides isomerization processes, our company is using self-control catalyst, success
Fixed bed-fluidized bed technique productions allyl alcohol lab scale craft is developed, but in the isomerization process, catalyst still can quickly lose
Living, fixed fluidized bed technique can not realize catalyst cyclic regeneration process, and fixed fluidized-bed reactor due to back-mixing it is serious, lead
Cause allyl alcohol selectivity to receive influence with epoxypropane conversion rate, be unfavorable for further industrialization amplification.
The content of the invention
For above-mentioned problems of the prior art, present inventor has made intensive studies, and as a result finds, uses
Wear-resistant catalyst, using riser fluidized-bed process, successfully solve in industrialization liquid phase method technique at present and solvent loss be present,
The problem of reaction time is grown, and side reaction is more, improves reactivity, reduces deactivation rate, while solve fixed bed
In fluidized-bed process back-mixing height cause product yield it is low with catalyst can not cyclic regeneration the problem of, obtained in the art compared with
Good application, reaction rate and selectivity have obtained effective raising.
A purpose of the invention is to provide a kind of new epoxides isomerization processes, using Circulating Fluidized Bed Process, into
The problem of work(solves and solvent loss in current liquid phase method technique be present, reaction time length, and side reaction is more.
Another object of the present invention is above-mentioned technique preparing corresponding allyl alcohol for propylene oxide isomerization, the work
Skill has high Atom economy, product yield and selectivity height, the free of contamination feature of technique, hence it is evident that better than current slurry bed system work
Skill.
To realize above technical purpose, the technical solution adopted by the present invention is as follows：
A kind of device of the continuous isomerization of epoxides, the device include：Two sections of riser fluidized-bed reactors, positioned at carrying
Settler above the second segment of riser fluidized-bed reactor, the catalyst being connected by pipeline with settler bottom regenerate system
System, the regenerated catalyst tank being connected by pipeline with catalyst regeneration system, regenerated catalyst tank are connected to by pipeline
The first paragraph of two sections of riser fluidized-bed reactors, wherein, each section of independent temperature control of two sections of riser fluidized-bed reactors is (i.e.
With single temperature-controlling system), the second segment part of two sections of riser fluidized-bed reactors is stretched into inside settler, what is stretched into
Catalyst deposit area is formed between the second segment part of two sections of riser reactors and the inwall of settler bottom, at the top of settler
Export and be provided with the reclaimable catalyst gas being used for settler bottom carbon deposition catalyst air lift for reacting product outlet, settler bottom
Carry pipeline.
The second segment part of the two sections of riser reactors stretched into inside settler can account for (or two sections of second segment riser
The second segment of riser fluidized-bed reactor) total length 1/5~4/5, preferably 2/5~3/5.
Preferably, settler bottom connects catalyst regeneration system by inclined tube.
The each section of independent temperature control on two sections of riser fluidized-bed reactors, it is preferable that two sections of riser fluid beds are anti-
The first paragraph (one section of riser) and second segment (two sections of risers) for answering device are provided with independent jacketed cooler, the chuck of first paragraph
The hot oil temperature of cooler be 210~270 DEG C, preferably 230~250 DEG C, riser fluidized-bed reactor lower semisection, material concentration
Height, reaction rate is fast, and rate of heat release is fast, and heat is removed as far as possible using low temperature deep fat；The heat of the jacketed cooler of second segment
Oil temperature is 250~290 DEG C, and preferably 270~280 DEG C, riser upper semisection, reaction rate reduces, and is added by high hot oil temperature
Heat, ensure upper semisection temperature, improve conversion ratio.
Filter, preferably 800-1200 mesh filter, such as 1000 mesh filters, major part are set at the top of the settler
Fine powder caused by abrasion will not be carried secretly into reaction gas at the top of settler during catalyst use, reduce catalyst and reaction
Liquid further series connection side reaction caused by contact.
Further, two sections of riser fluidized-bed reactors use slender type riser reactor, and aspect ratio is 50~
200：1, preferably 80~130:1, to reduce material back-mixing.
Further, recirculated water cooling is set in second segment (two sections of risers) the outlet top of riser fluidized-bed reactor
But device, the terminating reaction by 140~240 DEG C of control settlement device temperature, preferably 160~200 DEG C.
It is a further object to provide a kind of method of the continuous isomerization of epoxides, by reaction raw materials epoxidation
Thing is preheated to certain temperature (such as 220~350 DEG C, preferably 250~290 DEG C) with carrier gas nitrogen, allows raw material with being carried into two sections
Riser fluidized-bed reactor, contacted with the catalyst of fluidized state (regenerated catalyst and/or newly supplement catalyst), certain
Pressure (such as 0.1~5bar, it is preferable that 0.5~1.5bar；) under with the residence time (such as 1~10s, preferably 2~5s) two
Isomerization reaction is carried out in section riser fluidized-bed reactor, leg outlet obtains reaction product, raw material, carrier gas and catalyst
Mixture, isolated reaction gas and product in the settler on second segment top of two sections of riser fluidized-bed reactors is arranged at
C catalyst, wherein, reaction gas rises enters product separation system, settler bottom carbon distribution through reaction solution pipeline at the top of settler
Catalyst is made charcoal (such as with poor oxygen or air contact) after nitrogen air lift into regenerator regeneration, obtained regenerated flue gas
Discharged from regenerator overhead flue gas pipeline, obtained regenerated catalyst is delivered in regenerated catalyst storage tank, through catalyst
Pipeline returns to riser reactor.
Further, newly supplement catalyst make-up is into catalyst storage tank, for maintaining catalyst feed to balance.
Catalyst regeneration system is provided with regeneration nitrogen feeding line and regeneration air feed pipeline.
Preferably, two sections of riser fluidized-bed reactors use slender type riser reactor, and aspect ratio is 50~200：
1, preferably 80~130:1, reduce material back-mixing.
Unify by using two-stage riser reactor, accurate controlling reaction temperature, and simplify system, improve reliable
Property.
Preferably, first paragraph (one section of riser) cooler hot oil temperature of two sections of riser fluidized-bed reactors is 210
~270 DEG C, preferably 230~250 DEG C, riser reactor lower semisection, material concentration is high, and reaction rate is fast, and rate of heat release is fast, adopts
Heat is removed as far as possible with low temperature deep fat；
The cooler hot oil temperature of the second segment of two sections of riser fluidized-bed reactors be 250~290 DEG C, preferably 270~
280 DEG C, riser upper semisection, reaction rate reduces, and is heated by high hot oil temperature, ensures upper semisection temperature, improves conversion ratio.
In the inventive method, the second segment outlet top of two sections of riser fluidized-bed reactors sets circulating water
Device, by control settlement device temperature at 140~240 DEG C, preferably 160~200 DEG C and terminating reaction.
In the inventive method, settler bottom carries out air lift using nitrogen, is that settler lower catalytic agent deposition site is
Nitrogen atmosphere, reduces the further generation of side reaction in settler dead volume, and air lift nitrogen use level is 0.5 with epoxy ratio
~2:1, preferably 0.8~1.2:1(mol).
In the inventive method, filter is set, using 800-1200 mesh, the filtering of preferably 1000 mesh at the top of the settler
Device, fine powder caused by abrasion will not be carried secretly into reaction gas at the top of settler during most of catalyst use, and reduction is urged
Series connection side reaction caused by agent further contacts with reaction solution.
Preferably, the preheating temperature is 220~350 DEG C, preferably 250~290 DEG C.
Preferably, reaction pressure is 0.1~5bar, it is preferable that 0.5~1.5bar.
Preferably, the material and the catalyst time of contact in riser reactor are 1~10s, preferably 2~5s.
Preferably, newly the supplement ratio of supplement catalyst is 0.02~1%/h, preferably 0.05~0.2%/h.
In preferably, the mol ratio of nitrogen and epoxides is 1~5:1, preferably 2~3:1.
Preferably, the epoxides charging and catalyst quality ratio are 0.5~3：1, preferably 1~2:.
One or more of the epoxides in expoxy propane, epoxy butane, oxepane, 7-oxa-bicyclo[4.1.0.
Catalyst is urged using silica supported titanic oxide/zinc oxide/potassium hydroxide/lithium phosphate in the inventive method
Agent.
Heretofore described pressure is absolute pressure.
The positive effect of the present invention is：
The catalyst of the present invention prepares allyl alcohol for being catalyzed propylene oxide isomerization, and product yield significantly improves, one way
Yield reaches more than 50%, selectivity up to more than 94%；
Catalyst can be added with in-situ regeneration, and not introduce solvent, reduce solvent loss compared to slurry method technique, be improved
Process economy；
React decaying catalyst directly by inclined tube to be entered in regenerator, even if catalyst inactivation is fast, still realize continuous raw
Production；
Using lifting tubular type fluidized-bed reactor, material is fixed with catalyst contact time, and residence time destribution is narrow, passes through
External jacket controls temperature, and reaction temperature is stable, and side reaction control can reach fixed bed reactors level；
The technique green non-pollution, Atom economy is high, and main reaction Atom economy reaches 100%.
Riser reactor heat-tranferring system, settler remove hot terminating reaction system, change original riser reactor without
Heat is removed, the shortcomings that reaction terminating is ineffective, the shortcomings that partial catalyst is carried secretly into reacting gas, further increases product
Yield.
Brief description of the drawings
Fig. 1 is that different catalysts additional amount influences on reactivity worth.
Fig. 2 is the schematic device of the continuous isomerization of epoxides of the present invention.
1. reaction raw materials feeding line, the supplement charging of 2. fresh catalysts, 3. reaction gas outlet lines, 4. regeneration nitrogens enter
Expects pipe line, 5. regeneration air feed pipelines, tail gas discharge nozzle line after 6. regeneration, 7. reclaimable catalyst air lift pipelines, 8. coolers
Recirculated water is fed, and the discharging of 9. cooler recirculated waters, 10. 2 sections of riser fluidized-bed reactors, 11. settlers, 12. catalyst are again
Raw system (regenerator), 13. decaying catalyst feed-lines, 14. regenerated catalyst feed-lines, 15. 1 sections of risers are cold
But device deep fat is fed, and 16. 1 sections of lifting reactor deep fat dischargings, 17. 2 sections of riser cooler deep fat chargings, 18. 2 sections cold
But device deep fat discharges.
Embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples, it is necessary to explanation, embodiment not structure
The limitation of the paired claimed scope of the invention.
As shown in figure 1, the device of the continuous isomerization of epoxides of the present invention includes：Two sections of riser fluidized-bed reactors
10th, the settler 11 above the second segment of riser fluidized-bed reactor 10, by decaying catalyst feed-line 13 with
It is catalyzed after the catalyst regeneration system 12 of the bottom of settler 11 connection, the regeneration being connected by pipeline with catalyst regeneration system 12
Agent tank, regenerated catalyst tank are connected to two sections of riser fluidized-bed reactions by regenerated catalyst feed-line 14 (inclined tube)
The first paragraph of device 10, wherein, the bottom of the first paragraph of two sections of riser fluidized-bed reactors 10 is provided with reaction raw materials feeding line
1, each section of independent temperature control, the second segment part of two sections of riser fluidized-bed reactors 10 is stretched into inside settler 11, is being stretched into
The second segment part of two sections of riser reactors and the inwall of settler bottom between form catalyst deposit area, settler 11
Top is provided with reaction gas outlet line 3, and the bottom of settler 11, which is provided with, to be used for the to be generated of settler bottom carbon deposition catalyst air lift
Catalyst air lift pipeline 7.
The second segment part of the two sections of riser reactors stretched into inside settler can account for (or two sections of second segment riser
The second segment of riser fluidized-bed reactor) total length 1/5~4/5, preferably 2/5~3/5.
The first paragraph (one section of riser) and second segment (two sections of risers) of two sections of riser fluidized-bed reactors are provided with only
Vertical jacketed cooler, the jacketed cooler of first paragraph are respectively equipped with one section of riser cooler deep fat charging 15 and one section of lifting
Reactor deep fat discharging 16, hot oil temperature be 210~270 DEG C, preferably 230~250 DEG C, riser fluidized-bed reactor lower half
Section, material concentration is high, and reaction rate is fast, and rate of heat release is fast, and heat is removed as far as possible using low temperature deep fat；The chuck of second segment
Cooler is provided with two sections of riser cooler deep fats and feeds 17 and two-step cooling device deep fat discharging 18, and hot oil temperature is 250~290
DEG C, preferably 270~280 DEG C, riser upper semisection, reaction rate reduces, and is heated by high hot oil temperature, ensures upper semisection temperature
Degree, improve conversion ratio.
1000 mesh filters are set at the top of the settler, and fine powder caused by abrasion is not during most of catalyst use
It can carry secretly into reaction gas at the top of settler, reduce series connection side reaction caused by catalyst further contacts with reaction solution.
Two sections of riser fluidized-bed reactors use slender type riser reactor, and aspect ratio is 50~200：1, preferably 80
~130:1, to reduce material back-mixing.
Water recirculator is set in second segment (two sections of risers) the outlet top of riser fluidized-bed reactor, it has
There are cooler recirculated water charging 8 and cooler recirculated water discharging 9, by 140~240 DEG C of control settlement device temperature, preferably 160~
200 DEG C and terminating reaction.
Catalyst regeneration system 12 is provided with regeneration nitrogen feeding line 4 and regeneration air feed pipeline 5, carbon deposition catalyst warp
Contacted again with the air (poor oxygen) entered by regeneration air feed pipeline 5 into catalyst regeneration system 12 after nitrogen air lift
Raw burn charcoal, tail gas discharge nozzle line 6 is discharged after obtained regenerated flue gas regenerates from the top of catalyst regeneration system 12.
Regenerated catalyst tank is provided with fresh catalyst supplement charging 2.
In the examples below, as without especially indicating, used " % " is " wt% ".Product form uses Shimadzu
GC-2010 types gas chromatograph (PONA type capillary chromatographic columns, hydrogen flame detector, nitrogen is as carrier gas) is analyzed.Adopt
With alcohol solvent, 250 DEG C of temperature of vaporization chamber, flow rate of carrier gas 1ml/min, μ l of sample size 1, chromatogram column and programmed temperature：50 DEG C first
2min is kept, is then warming up to 80 DEG C with 5 DEG C/min, keeps 5min, is then warming up to 260 DEG C with 20 DEG C/min, is kept
15min。
The catalyst used in embodiment is prepared as follows：
By 1000g lithium phosphate catalyst originals powder, 4000g Ludox (electronic-grade silica sol, 10~20nm of average grain diameter, gold
Belong to ion concentration ＜ 20ppm, solid content 25%, pH=8, Shandong Bai Te new materials Co., Ltd), 33.3g titanium dioxide,
16.7g zinc oxide, 2.5g potassium hydroxide mixing, adds 1000g deionized waters, stirs, and acquisition is not spray-dried slurry
Material, slurry contain 34% admittedly.Slurry is squeezed into spray dryer and is spray-dried, 250 DEG C of spray drying temperature.After being spray-dried
Particle is put into 360 DEG C of roasting 6h in Muffle furnace, obtains finished catalyst ISO-1.Catalyst composition is as follows：
(TiO2)1.62(ZnO)0.82(KOH)0.12(Li3PO4)48.72(SiO2)48.72。
Embodiment 1
For the reactor used in this technique for two sections of riser fluidized-bed reactors as shown in Figure 1, its internal diameter is 40 millis
Rice, is highly 4 meters；Realize that catalyst and reactant and product are fast in settler in the second segment outlet of riser reactor
Speed separation, reaction product are sent into subsequent separation system.
Nitrogen, expoxy propane are heated into 280 DEG C first to connect into riser and regenerated catalyst and new supplement catalyst
Reaction, nitrogen flow 10L/min are touched, propylene oxide feed speed is 7.8kg/h, recycling catalyst 3.9kg/h, supplements catalyst
Feed rate 3.9g/h, jacketed 280 DEG C of conduction oil temperature outside riser, when material contacts with catalyst in riser reactor
Between be 3 seconds, outlet temperature of riser is 290 DEG C, and outlet reaction solution and catalyst mixture can be but to 180 DEG C, instead through heat exchanger
It should terminate.
The carbon deposition catalyst of leg outlet enters settler under gravity, and settler internal diameter is 200 millimeters, height
For 1.5 meters；For carbon deposition catalyst through nitrogen air lift in settler, air lift nitrogen use level is 5L/min, is entered after catalyst sedimentation
Regenerator regenerates, and the catalyst after regeneration returns to riser reactor；Reaction gas rises to reaction gas outlet at the top of settler
Enter subsequent separation system after condensation.
Reaction solution samples after condensation, is analyzed through GC, analysis result is shown in Table 1.
Table 1：The product liquid analysis result of embodiment 1
| React group | PO/% | AA/% | Other/% | XPO/ % | SAA/ % |
| R-1 | 43.25 | 53.67 | 3.08 | 56.75 | 94.57 |
Note：
Embodiment 2
As different from Example 1, isomerization performance under different preheating temperatures has been investigated.It is shown in Table 2.
Table 2：Different temperatures reactivity worth result
| Preheating temperature/DEG C | PO/% | AA/% | Other/% | XPO/ % | SAA/ % |
| 250 | 68.12 | 30.51 | 1.37 | 31.88 | 95.70 |
| 260 | 60.54 | 37.53 | 1.93 | 39.46 | 95.11 |
| 270 | 51.31 | 46.12 | 2.57 | 48.69 | 94.72 |
| 280 | 43.25 | 53.67 | 3.08 | 56.75 | 94.57 |
| 290 | 27.45 | 66.71 | 5.84 | 72.55 | 91.95 |
Embodiment 3
Influence of the different chilling temperatures to end reaction performance has been investigated as different from Example 1, is shown in Table 3.
Table 3：Different chilling temperature reactivity worth
Embodiment 4
Influence of the different times of contact to end reaction performance has been investigated as different from Example 1, is shown in Table 4.
The different contact time reaction performances of table 4
| Time of contact/s | PO/% | AA/% | Other/% | XPO/ % | SAA/ % |
| 2 | 55.76 | 42.71 | 1.53 | 44.24 | 96.54 |
| 3 | 43.25 | 53.67 | 3.08 | 56.75 | 94.57 |
| 4 | 36.41 | 59.23 | 4.36 | 63.59 | 93.14 |
| 5 | 31.66 | 62.53 | 5.81 | 68.34 | 91.50 |
Embodiment 5
Different epoxides have been investigated as different from Example 1 compares the shadow of end reaction performance with catalyst quality
Ring, be shown in Table 5.
The different catalysts dosage of table 5
| Epoxy/catalyst | PO/% | AA/% | Other/% | XPO/ % | SAA/ % |
| 1 | 65.76 | 33.32 | 0.92 | 34.24 | 97.31 |
| 1.3 | 56.25 | 41.89 | 1.86 | 43.75 | 95.75 |
| 1.8 | 47.23 | 50.23 | 2.54 | 52.77 | 95.19 |
| 2 | 43.25 | 53.67 | 3.08 | 56.75 | 94.57 |
Note：Epoxy/catalyst is charge-mass ratio.
Embodiment 6
Not influence of the catalyst additional amount to reactivity worth has been investigated as different from Example 1, sees Fig. 1.
Claims (12)
1. a kind of device of the continuous isomerization of epoxides, the device include：Two sections of riser fluidized-bed reactors, positioned at lifting
Settler above the second segment of pipe fluidized-bed reactor, the catalyst regeneration system being connected by pipeline with settler bottom,
The regenerated catalyst tank being connected by pipeline with catalyst regeneration system, regenerated catalyst tank are connected to two sections by pipeline
The first paragraph of riser fluidized-bed reactor, wherein, each section of independent temperature control of two sections of riser fluidized-bed reactors, two sections carry
The second segment part of riser fluidized-bed reactor is stretched into inside settler, in the second segment portion of the two sections of riser reactors stretched into
The formation catalyst deposit area point the inwall of settler bottom between, settler top exit are reacting product outlet, settler
Bottom is provided with the reclaimable catalyst air lift pipeline being used for settler bottom carbon deposition catalyst air lift.
2. device according to claim 1, it is characterised in that the of the two sections of riser reactors stretched into inside settler
Two sections of parts account for the 1/5~4/5 of second segment riser total length, and preferably 2/5~3/5.
3. device according to claim 1 or 2, it is characterised in that the first paragraph of two sections of riser fluidized-bed reactors and
Second segment is provided with independent jacketed cooler, and the hot oil temperature of the jacketed cooler of first paragraph is 210~270 DEG C, preferably 230~
250℃；The hot oil temperature of the jacketed cooler of second segment is 250~290 DEG C, preferably 270~280 DEG C.
4. according to the device described in any one of claim 1-3, it is characterised in that set filtering at the top of the settler
Device, preferably 800-1200 mesh filter, such as 1000 mesh filters.
5. according to the device described in any one of claim 1-4, it is characterised in that two sections of riser fluidized-bed reactors are adopted
With slender type riser reactor, aspect ratio is 50~200：1, preferably 80~130:1.
6. according to the device described in any one of claim 1-5, it is characterised in that the of riser fluidized-bed reactor
Water recirculator is set above second stage exit, by 140~240 DEG C of control settlement device temperature, preferably 160~200 DEG C eventually
Only react.
7. a kind of method of the continuous isomerization of epoxides, this method is included reaction raw materials epoxides, pre- with carrier gas nitrogen
Heat allows raw material with entering two sections of riser fluidized-bed reactions to certain temperature (such as 220~350 DEG C, preferably 250~290 DEG C)
Device, contacted with the catalyst of fluidized state, in certain pressure (such as 0.1~5bar, it is preferable that 0.5~1.5bar；) with stopping
Under time (such as 1~10s, preferably 2~5s) isomerization reaction, leg outlet are carried out in two sections of riser fluidized-bed reactors
The mixture of reaction product, raw material, carrier gas and catalyst is obtained, is being arranged at the second segment of two sections of riser fluidized-bed reactors
Isolated reaction gas and carbon deposition catalyst in the settler on top, wherein, reaction gas rises through reaction liquid pipe at the top of settler
Line enters product separation system, settler bottom carbon deposition catalyst after nitrogen air lift, into regenerator regeneration make charcoal (such as with
Poor oxygen or air contact), obtained regenerated flue gas is discharged from regenerator overhead flue gas pipeline, and obtained regenerated catalyst is defeated
Deliver in regenerated catalyst storage tank, riser reactor is returned through catalyst line.
8. according to the method for claim 7, it is characterised in that new supplement catalyst make-up is used for into catalyst storage tank
Maintain catalyst feed balance.
9. according to the method for claim 7, it is characterised in that the first paragraph cooler of two sections of riser fluidized-bed reactors
Hot oil temperature is 210~270 DEG C, preferably 230~250 DEG C；
The cooler hot oil temperature of the second segment of two sections of riser fluidized-bed reactors be 250~290 DEG C, preferably 270~280
℃。
10. according to the method any one of claim 7-9, it is characterised in that two sections of riser fluidized-bed reactors
Second segment outlet top sets water recirculator, by control settlement device temperature at 140~240 DEG C, preferably 160~200 DEG C
And terminating reaction.
11. according to the method any one of claim 7-10, it is characterised in that air lift nitrogen use level rubs with epoxides
You are than being 0.5~2:1, preferably 0.8~1.2:1.
12. according to the method any one of claim 7-11, it is characterised in that
Preheating temperature is 220~350 DEG C, preferably 250~290 DEG C；And/or
Reaction pressure is 0.1~5bar, it is preferable that 0.5~1.5bar；And/or
The material and the catalyst time of contact in riser reactor are 1~10s, preferably 2~5s；And/or
The supplement ratio of new supplement catalyst is 0.02~1%/h, preferably 0.05~0.2%/h；And/or
The mol ratio of nitrogen and epoxides is 1~5:1, preferably 2~3:1；And/or
The epoxides charging and catalyst quality ratio are 0.5~3：1, preferably 1~2:1；And/or
One or more of the epoxides in expoxy propane, epoxy butane, oxepane, 7-oxa-bicyclo[4.1.0；And/or
Catalyst uses silica supported titanic oxide/zinc oxide/potassium hydroxide/lithium phosphate catalyst.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357242A (en) * | 2018-04-10 | 2019-10-22 | 中国石油化工股份有限公司 | A kind of processing method of fluidized catalytic oxidation treatment device and saline sewage |
| CN115894400A (en) * | 2022-12-01 | 2023-04-04 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane by directly oxidizing chloropropene by using liquid-solid circulating fluidized bed reactor |
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| CN204848257U (en) * | 2015-06-25 | 2015-12-09 | 中国石油天然气集团公司 | Device of methane catalytic cracking production hydrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN204848257U (en) * | 2015-06-25 | 2015-12-09 | 中国石油天然气集团公司 | Device of methane catalytic cracking production hydrogen |
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| 马卫华等: "环氧丙烷异构化产物的表征与反应机理", 《工业催化》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357242A (en) * | 2018-04-10 | 2019-10-22 | 中国石油化工股份有限公司 | A kind of processing method of fluidized catalytic oxidation treatment device and saline sewage |
| CN115894400A (en) * | 2022-12-01 | 2023-04-04 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane by directly oxidizing chloropropene by using liquid-solid circulating fluidized bed reactor |
| CN115894400B (en) * | 2022-12-01 | 2024-02-02 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane by directly oxidizing chloropropene by using liquid-solid circulating fluidized bed reactor |
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