CN107417660A - A kind of device, technique and the solid catalyst of vapor phase method synthesizing acrylic ester - Google Patents
A kind of device, technique and the solid catalyst of vapor phase method synthesizing acrylic ester Download PDFInfo
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- CN107417660A CN107417660A CN201710234814.5A CN201710234814A CN107417660A CN 107417660 A CN107417660 A CN 107417660A CN 201710234814 A CN201710234814 A CN 201710234814A CN 107417660 A CN107417660 A CN 107417660A
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- Prior art keywords
- shell
- tube
- acrylic ester
- vapor phase
- tube reactor
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- 238000000034 method Methods 0.000 title claims abstract description 64
- -1 acrylic ester Chemical class 0.000 title claims abstract description 35
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 31
- 239000012808 vapor phase Substances 0.000 title claims abstract description 27
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 51
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 43
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 36
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000001294 propane Substances 0.000 claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 12
- 239000010409 thin film Substances 0.000 claims abstract description 9
- 229960004424 carbon dioxide Drugs 0.000 claims description 25
- 230000004087 circulation Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000013461 design Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 30
- 230000008569 process Effects 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 11
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical group [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- 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
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of device of vapor phase method synthesizing acrylic ester, including shell and tube mixing preheater, shell and tube reactor, flash tank and conduction oil storage tank, solid catalyst is filled with shell and tube reactor.The invention discloses a kind of technique of vapor phase method synthesizing acrylic ester, gas phase carbon dioxide and the blended preheating of expoxy propane（60 DEG C, 0.6Mpa）Reacted into shell and tube reactor, from shell and tube reactor bottom discharge, into flash tank, enter back into the evaporation purification of thin film evaporator system.A kind of solid catalyst, it is using porous columnar ceramic as carrier, is loaded with KI, potassium carbonate and sodium carbonate thereon, the mass ratio of KI, potassium carbonate and sodium carbonate three is 20:40:40.The technique of the vapor phase method synthesizing acrylic ester of the present invention, has the advantages that reaction pressure is low, reaction temperature is low, side reaction is few, catalyst service life is long, technological process is short, floor space is small, products obtained therefrom quality is high.
Description
Technical field
The present invention relates to a kind of device of vapor phase method synthesizing acrylic ester, technique and solid catalyst used, belong to
Chemical technology field.
Background technology
It is certain proportion that traditional carbon dioxide and expoxy propane, which produces propene carbonate technique (flow chart is as shown in Figure 3),
Carbon dioxide, expoxy propane, polyethylene glycol make the KI liquid-phase catalyst of carrier and be pumped into first and second reaction by measuring pump
Device, temperature of reactor are 180~220 DEG C, and reactor pressure is 4.5Mpa or so.At the top of expoxy propane and the reacted device of catalyst
Enter first reactor with circulation fluid, 3 points of the reacted device upper, middle and lower of carbon dioxide enter reactor, carbon dioxide and epoxy
The mixed liquor of propane and catalyst is inversely to contact in reactor, and circulation fluid extracts warp out from the point of reactor upper, middle and lower three
Outer cooling tubulation spraying cooling maintenance reaction device temperature is at 180~220 DEG C.Reaction solution enters the second reaction through first reactor
Device, then it is discharged to flash tank through second reactor.The feed liquid for being put into flash tank enters back into thin film evaporator system progress carbonic acid third
Alkene ester purifies, and the fine work propene carbonate of content more than 99.95% is made.The reaction process is continuous feed and continuous discharge side
Formula.The reaction process has as a drawback that：
1. reaction pressure is high, system response pressure is 4.5Mpa or so, and this requires reactor to use third class(grade) pressure vessel
Production method, dnockout pumps use diaphragm metering pump, high to equipment requirement, and one-time investment is big.
2. reaction temperature is high, at 180~220 DEG C, system thermal must be protected system response temperature by outer circulation cooling
Hold, power consumption is high.
3. side reaction is more, because temperature of reactor is high, causes chemical reaction side reaction more, have the generation of the polymer of ring third, no
But wastage of material is caused, and influences product quality.
4. catalyst deactivation is fast, because system response temperature is high, side reaction is more, and catalyst recycles and reuses, temperature
Height causes catalyst to polymerize division repeatedly, and catalyst inactivation is fast, and usage time is short, and reaction cost increases, catalyst service life
It is average three months.6000 tons of propene carbonate products of a collection of 20 tons of production of catalyst must be changed.
5. production process reaction is incomplete, smell is big, and in particular to the catalyst later stage, reaction effect is bad, not only wastes
Raw material, consumption is high, and unreacted feed carbon dioxide and expoxy propane and the low component materials of generation are overflowed in flash tank
Smell is very big.
6. technological process is grown, floor space is big.
7. because catalyst change is frequent, amount is big, it is chemical waste, influences environmental protection；And flash tank overflows the gas phase of coming
Material can not recycle.
Based on disadvantages mentioned above, it is necessary to research and develop a kind of reaction pressure is low, reaction temperature is low, side reaction is few, catalyst use
Long lifespan, the device for the synthesizing acrylic ester that technological process is short, floor space is small, product quality is high and technique.
The content of the invention
For above-mentioned prior art, in order to promote industry progress, reach energy-conservation, emission reduction, environmental protection, purposes of safety, this hair
It is bright to provide a kind of device and technique of vapor phase method synthesizing acrylic ester, the technique have reaction pressure is low, reaction temperature is low,
The advantages that side reaction is few, catalyst service life is long, technological process is short, floor space is small, products obtained therefrom quality is high.The present invention is also
Provide a kind of solid catalyst for vapor phase method synthesizing acrylic ester --- the alkaline column solid particle catalysis containing iodine
Agent.
The present invention is achieved by the following technical solutions：
A kind of device of vapor phase method synthesizing acrylic ester, including shell and tube mixing preheater, shell and tube reactor, flash distillation
Tank and conduction oil storage tank, wherein, the top of shell and tube mixing preheater connects with the top of shell and tube reactor, shell and tube mixing
The top of preheater connects with the bottom of shell and tube reactor；The bottom of shell and tube reactor connects with flash tank；Circulating fan
Connected with the top of flash tank with the bottom of shell and tube mixing preheater, the pipeline of connection is provided with circulating fan；Conduction oil stores up
Groove connects between the pipe of shell and tube mixing preheater, between the pipe of shell and tube reactor (be used for interior circulating heat conduction oil) respectively, connection
Pipeline be provided with circulating pump.
Preferably, the shell and tube mixing preheater, diameter 1.2m, high 2m, takes lower public attention, design pressure is
1.0Mpa。
Preferably, the shell and tube reactor, diameter 2m, high 6m, lower public attention, design pressure 1.2Mpa, Mei Gelie are taken
Pipe diameter is 32mm, and tubulation bottom is provided with spring using the support as solid catalyst.
Preferably, the volume of the conduction oil storage tank is 20m3。
Preferably, the circulating fan is internal circulating load for 30m per hour3Axle stream circulating fan.
A kind of technique of vapor phase method synthesizing acrylic ester, utilizes said apparatus synthesizing acrylic ester, including following step
Suddenly：
(1) preheat：Conduction oil is provided with conduction oil storage tank, heat conduction oil temperature open the circulation pump, is followed at 60 DEG C ± 3 DEG C
Ring conduction oil, shell and tube mixing preheater, shell and tube reactor are preheated；
Preferably, the conduction oil, can be from Synthesis of dimethyl carbonate system import part conduction oil (200 DEG C of temperature), its
Mixed with the conduction oil in deep fat storage tank, adjust the temperature to 60 DEG C ± 3 DEG C；
(2) feed：Carbon dioxide, expoxy propane after preheated mixing, mix from shell and tube mixing preheater bottom feed
Material is controlled in 0.55~0.6Mpa from top discharge, top gas phase outlet pressure；
Preferably, during charging, carbon dioxide enters shell and tube mixing preheater bottom by measuring pump, and expoxy propane passes through
Canned motor pump flowmeter is pumped into shell and tube mixing preheater bottom；
Preferably, the charge proportion of carbon dioxide and expoxy propane is 66:58 (mass ratioes)；
Preferably, the charging rate of carbon dioxide is 0.225m per hour3, the charging rate of expoxy propane is per hour
0.233m3(by 5 tons of calculating of production propene carbonate daily)；
(3) react：Compound (for temperature at 60 DEG C, pressure is in 0.6Mpa) enters from the top discharge of shell and tube mixing preheater
Shell and tube reactor, reacted, temperature is at 120 DEG C ± 3 DEG C in control shell and tube reactor；It is filled with shell and tube reactor
Solid catalyst (loading catalyst is uniform, and dress is real, fills, drag uniform)；
(4) unreacted carbon dioxide, expoxy propane enter shell and tube mixing preheater from shell and tube reactor bottom；Instead
Should after material enter flash tank from shell and tube reactor bottom discharge, ON cycle blower fan, then gas phase portion (unreacted two
Carbonoxide and expoxy propane) enter the circulation participation reaction of shell and tube mixing preheater under circulating fan effect, liquid phase part enters
Enter thin film evaporator and carry out distilation；Flash tank bottom connects with thin film evaporator.
A kind of solid catalyst, it is with porous columnar ceramic (Φ for the alkaline column solid particle catalyst containing iodine
5mm × 8mm, cylindrical ceramic catalyst carrier, 5 millimeters of diameter are high 10 millimeters) it is carrier, KI, carbonic acid are loaded with thereon
Potassium and sodium carbonate.The mass ratio of KI, potassium carbonate and sodium carbonate three is 18~22:38~42:38~42, preferably 20:40:
40。
The solid catalyst is prepared by the following method to obtain：KI, potassium carbonate and sodium carbonate are pressed into quality
Than for 18~22:38~42:38~42 (preferably 20:40:40) it is dissolved in water, it is molten that porous columnar ceramic is dipped into mixing
In liquid, soak 22~26 hours；Then slowly heat and be evaporated water, columnar ceramic is placed in crucible, then be placed in baking oven and roast
Burn, roasting divides three phases：1. 30~150 DEG C, 4 hours；2. 150~250 DEG C, 6 hours；It is 3. 250~40 DEG C, 2 small
When；Produce.
The solid catalyst of the present invention, compared with KI liquid-phase catalyst of the prior art, the gentle (nothing of reaction condition
Need HTHP) (raw catalyst main component is that polyethylene glycol is carrier, and the mass ratio of KI and potassium carbonate is 100:1, rise
Major catalytic effect is iodide ion under weak basic condition, under normal production conditions, iodide ion proportion in reactor
About 5% or so, content is very low.And the solid basic catalyst of the present invention, not only contain sodium carbonate, also added carbonic acid
Potassium, both constitute about 80% of total content or so at ratio, considerably increase the alkalescence condition of catalytic reaction, the most key,
Iodate potassium content greatly improves, and accounts for the 20% of total catalysis high content, under normal reaction conditions, catalyst iodate potassium content by
5% brings up to 20%, not only strengthens alkalescence condition, also substantially increases iodate potassium content, so changing reaction condition),
Catalytic activity is good, and (first, using porous ceramics, for carrier, specific surface area is big, makes catalyst abundant with reaction mass in the unit interval
Contact, substantially increases reaction effect；Second, under normal reaction conditions, catalyst iodate potassium content is brought up to by 5%
20%), cheap (reducing by 25 yuan using ton cost), service life length (can use 2 years), can activate (method of activation and
Preparation method is identical), half a year activates a catalyst activity and not subtracted, and waste catalyst is solid inorganic thing, is not harmful influence, just
In processing.
The technique of the vapor phase method synthesizing acrylic ester of the present invention, a certain proportion of gas phase carbon dioxide and expoxy propane warp
Mixing is preheating to 60 DEG C, pressure 0.6Mpa, (is filled with the alkaline column solid particle containing iodine in it to urge into shell and tube reactor
Agent), reaction temperature is controlled at 120 DEG C, from shell and tube reactor bottom discharge, the unreacted titanium dioxide flashed through flash tank
Warm-up cycle is reacted again for carbon and expoxy propane, and the feed liquid after flash distillation enters the evaporation purification of thin film evaporator system.
The device of the vapor phase method synthesizing acrylic ester of the present invention, compared with prior art, using low pressure, low temperature
Shell and tube reactor substitutes two high pressure-temperature outer circulations to cool reactor, and substituting polyethylene glycol using solid catalyst contains
Iodine solution mutually recycles catalyst.The technique of the vapor phase method synthesizing acrylic ester of the present invention, have reaction pressure low
(0.6Mpa), reaction temperature low (120 DEG C), side reaction few (reaction temperature is low, and side reaction is few), catalyst service life length are (anti-
Answer temperature low, catalyst inactivation is slow), the advantages that technological process is short, floor space is small, products obtained therefrom quality is high, safety, environmental protection,
Energy-conservation, greatly reduces production cost, has the very strong market competitiveness.The solid catalyst of the present invention, service life length, one
Year change once, ton price is not belonging to hazardous chemical than existing 600 yuan or so of catalyst degradation, from basic
On promote the development and industry progress of industry.
Brief description of the drawings
Fig. 1：The schematic device of the vapor phase method synthesizing acrylic ester of the present invention.
Fig. 2：The process flow diagram of the vapor phase method synthesizing acrylic ester of the present invention.
It is 1. shell and tube mixing preheater in Fig. 1, Fig. 2；2. it is shell and tube reactor；3. it is flash tank；4. it is circulated air
Machine；5. it is conduction oil storage tank；6. it is circulating pump.
Fig. 3：The process flow diagram of synthesizing acrylic ester in the prior art.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Involved instrument, reagent, material etc. in following embodiments, it is existing in the prior art unless otherwise noted
Conventional instrument, reagent, material etc., can be obtained by regular commercial sources.Involved experimental method in following embodiments, inspection
Survey method etc., it is existing normal experiment method, detection method etc. in the prior art unless otherwise noted.
The vapor phase method synthesizing acrylic ester of embodiment 1
Equipment therefor structure is as shown in figure 1, be the 15000 tons of propene carbonate production dresses of annual output possessed in applicant
Transformed on the basis of putting, its structure is：Stored up including shell and tube mixing preheater, shell and tube reactor, flash tank and conduction oil
Groove (volume 20m3), wherein, the top of shell and tube mixing preheater connects with the top of shell and tube reactor, and shell and tube mixing is pre-
The top of hot device connects with the bottom of shell and tube reactor；The bottom of shell and tube reactor connects with flash tank；Circulating fan with
The top of flash tank connects with the bottom of shell and tube mixing preheater, and the pipeline of connection (is for internal circulating load provided with circulating fan
30m per hour3Axle stream circulating fan)；Conduction oil storage tank is respectively between the pipe of shell and tube mixing preheater, shell and tube reactor
Pipe between connect (being used for interior circulating heat conduction oil), the pipeline of connection is provided with circulating pump.
The shell and tube mixing preheater, diameter 1.2m, high 2m, takes lower public attention, design pressure 1.0Mpa.
The shell and tube reactor, diameter 2m, high 6m take lower public attention, design pressure 1.2Mpa, and each tubulation is a diameter of
32mm, tubulation bottom are provided with spring using the support as solid catalyst.
The step of vapor phase method synthesizing acrylic ester, is following (flow is as shown in Figure 2)：
(1) preheat：Conduction oil is provided with conduction oil storage tank, from Synthesis of dimethyl carbonate system import part conduction oil (temperature
200 DEG C of degree), it is mixed with the conduction oil in deep fat storage tank, makes heat conduction oil temperature at 60 DEG C, open the circulation pump, circulating heat conduction oil,
Shell and tube mixing preheater, shell and tube reactor are preheated；
(2) feed：Carbon dioxide, expoxy propane are fast from shell and tube mixing preheater bottom feed, the charging of carbon dioxide
Spend for 0.225m per hour3, the charging rate of expoxy propane is 0.233m per hour3(based on daily 5 tons of propene carbonate of production
Calculate)；After preheated mixing, compound is controlled in 0.6Mpa from top discharge, top gas phase outlet pressure；
Carbon dioxide enters shell and tube mixing preheater bottom by measuring pump, and expoxy propane passes through canned motor pump flowmeter pump
Fall in lines tubular-mix preheater bottom；
(3) react：Compound (for temperature at 60 DEG C, pressure is in 0.6Mpa) enters from the top discharge of shell and tube mixing preheater
Shell and tube reactor, reacted, temperature is at 120 DEG C ± 3 DEG C in control shell and tube reactor；It is filled with shell and tube reactor
Solid catalyst；
The solid catalyst, it is with porous columnar ceramic (5 millis for the alkaline column solid particle catalyst containing iodine
Rice × 8 millimeters) it is carrier, it is loaded with KI, potassium carbonate and sodium carbonate thereon, KI, potassium carbonate and sodium carbonate three
Mass ratio is 20:40:40, it is prepared by the following method to obtain：It is in mass ratio by KI, potassium carbonate and sodium carbonate
20:40:40 are dissolved in water, and porous columnar ceramic is dipped into mixed solution, are soaked 24 hours；Then slowly heating will
Water is evaporated, and columnar ceramic is placed in crucible, then is placed in baking oven and is calcined, and roasting divides three phases：It is 1. 30~150 DEG C, 4 small
When；2. 150~250 DEG C, 6 hours；3. 250~40 DEG C, 2 hours；Produce.
(4) unreacted carbon dioxide, expoxy propane enter shell and tube mixing preheater from shell and tube reactor bottom；Instead
Should after material enter flash tank from shell and tube reactor bottom discharge, ON cycle blower fan, then gas phase portion (unreacted two
Carbonoxide and expoxy propane) enter the circulation participation reaction of shell and tube mixing preheater under circulating fan effect, liquid phase part enters
Enter thin film evaporator and carry out distilation；Flash tank bottom connects with thin film evaporator.
Product after purification, sampling analysis, propylene carbonate ester content are 99.9%, belong to top grade product.
The technique and technique of the prior art of the Comprehensive Correlation present invention, it is found that device and process safety of the invention can
Lean on, temperature of charge, pressure and reactor temperature, pressure control very well, and sampling Detection product quality has also obtained very big
Improve, directly reach top grade product, flash drum overhead gaseous phase materials are stable, and internal circulating load is stable, process stabilizing.
The vapor phase method synthesizing acrylic ester of embodiment 2
With embodiment 1, difference is for device, technique：The charging rate of carbon dioxide is 0.455m per hour3, ring
The charging rate of Ethylene Oxide is 0.467m per hour3(by 10 tons of calculating of production propene carbonate daily).
Products obtained therefrom sampling analysis, propylene carbonate ester content are 99.95%, belong to top grade product.
The vapor phase method synthesizing acrylic ester of embodiment 3
With embodiment 1, difference is for device, technique：The charging rate of carbon dioxide is 0.677m per hour3, ring
The charging rate of Ethylene Oxide is 0.701m per hour3(by 15 tons of calculating of production propene carbonate daily).
Products obtained therefrom sampling analysis, propylene carbonate ester content are 99.99%, belong to LITHIUM BATTERY top grade product, production scene is almost
Without chemical odor, low-pressure low-temperature ensure that process safety, and various parameters situation of change is stable, all within controlled range.
Although above-mentioned the embodiment of the present invention is described in conjunction with the embodiments, not the present invention is protected
The limitation of scope, one of ordinary skill in the art should be understood that on the basis of technical scheme, those skilled in the art
Various modifications or deformation that creative work can make need not be paid still within protection scope of the present invention.
Claims (10)
- A kind of 1. device of vapor phase method synthesizing acrylic ester, it is characterised in that：It is anti-including shell and tube mixing preheater, shell and tube Device, flash tank and conduction oil storage tank are answered, wherein, the top of shell and tube mixing preheater connects with the top of shell and tube reactor, The top of shell and tube mixing preheater connects with the bottom of shell and tube reactor；The bottom of shell and tube reactor connects with flash tank It is logical；Circulating fan connects with the top of flash tank with the bottom of shell and tube mixing preheater, and the pipeline of connection is provided with circulated air Machine；Conduction oil storage tank connects between the pipe of shell and tube mixing preheater, between the pipe of shell and tube reactor respectively, on the pipeline of connection Provided with circulating pump.
- 2. the device of vapor phase method synthesizing acrylic ester according to claim 1, it is characterised in that：The shell and tube mixing Preheater, diameter 1.2m, high 2m, takes lower public attention, design pressure 1.0Mpa.
- 3. the device of vapor phase method synthesizing acrylic ester according to claim 1, it is characterised in that：The tubular reaction Solid catalyst is filled with device；The solid catalyst, it is using porous columnar ceramic as carrier, is loaded with iodate thereon Potassium, potassium carbonate and sodium carbonate, the mass ratio of KI, potassium carbonate and sodium carbonate three is 18~22:38~42:38~42；It is It is prepared by the following method what is obtained：It is 18~22 in mass ratio by KI, potassium carbonate and sodium carbonate:38~42:38~42 It is dissolved in water, porous columnar ceramic is dipped into mixed solution, soaks 22~26 hours；Then slowly heat and steam water It is dry, columnar ceramic is placed in crucible, then be placed in baking oven and be calcined, roasting divides three phases：1. 30~150 DEG C, 4 hours； 2. 150~250 DEG C, 6 hours；3. 250~40 DEG C, 2 hours；Produce.
- 4. the device of the vapor phase method synthesizing acrylic ester according to claim 1 or 3, it is characterised in that：The shell and tube Reactor, diameter 2m, high 6m, lower public attention is taken, design pressure 1.2Mpa, each a diameter of 32mm of tubulation, tubulation bottom is provided with Spring.
- A kind of 5. technique of vapor phase method synthesizing acrylic ester, it is characterised in that：Using any one of Claims 1 to 44 Device synthesizing acrylic ester, comprise the following steps：(1) preheat：Conduction oil is provided with conduction oil storage tank, making heat conduction oil temperature, open the circulation pump, circulation is led at 60 DEG C ± 3 DEG C Deep fat, shell and tube mixing preheater, shell and tube reactor are preheated；(2) feed：Carbon dioxide, expoxy propane are from shell and tube mixing preheater bottom feed, after preheated mixing, compound from Top discharge, top gas phase outlet pressure are controlled in 0.55~0.6Mpa；(3) react：Compound enters shell and tube reactor from the top discharge of shell and tube mixing preheater, is reacted, control row Temperature is at 120 DEG C ± 3 DEG C in tubular reactor；Solid catalyst is filled with shell and tube reactor；The solid catalyst, it is using porous columnar ceramic as carrier, is loaded with KI, potassium carbonate and sodium carbonate thereon, The mass ratio of KI, potassium carbonate and sodium carbonate three is 18~22:38~42:38~42；It is to be prepared by the following method Arrive：It is 18~22 in mass ratio by KI, potassium carbonate and sodium carbonate:38~42:38~42 are dissolved in water, will be porous Columnar ceramic is dipped into mixed solution, is soaked 22~26 hours；Then slowly heat and be evaporated water, columnar ceramic is placed in earthenware In crucible, then it is placed in baking oven and is calcined, roasting divides three phases：1. 30~150 DEG C, 4 hours；It is 2. 150~250 DEG C, 6 small When；3. 250~40 DEG C, 2 hours；Produce；(4) unreacted carbon dioxide, expoxy propane enter shell and tube mixing preheater from shell and tube reactor bottom；After reaction Material enter flash tank from shell and tube reactor bottom discharge, ON cycle blower fan, then gas phase portion acted in circulating fan Lower to enter the circulation participation reaction of shell and tube mixing preheater, liquid phase part enters thin film evaporator and carries out distilation；Flash tank Bottom connects with thin film evaporator.
- 6. the technique of vapor phase method synthesizing acrylic ester according to claim 5, it is characterised in that：The carbon dioxide with The charge proportion of expoxy propane is 66:58, mass ratio.
- 7. the technique of vapor phase method synthesizing acrylic ester according to claim 5, it is characterised in that：The carbon dioxide Charging rate is 0.225m per hour3, the charging rate of expoxy propane is 0.233m per hour3；Or：The charging rate of carbonoxide For 0.455m per hour3, the charging rate of expoxy propane is 0.467m per hour3；Or：The charging rate of carbon dioxide is per small When 0.677m3, the charging rate of expoxy propane is 0.701m per hour3。
- A kind of 8. solid catalyst, it is characterised in that：It is using porous columnar ceramic as carrier, is loaded with KI, carbon thereon Sour potassium and sodium carbonate, the mass ratio of KI, potassium carbonate and sodium carbonate three is 18~22:38~42:38~42；Be by with Lower section method is prepared：It is 18~22 in mass ratio by KI, potassium carbonate and sodium carbonate:38~42:38~42 are dissolved in In water, porous columnar ceramic is dipped into mixed solution, soaked 22~26 hours；Then slowly heat and be evaporated water, will Columnar ceramic is placed in crucible, then is placed in baking oven and is calcined, and roasting divides three phases：1. 30~150 DEG C, 4 hours；②150 ~250 DEG C, 6 hours；3. 250~40 DEG C, 2 hours；Produce.
- 9. solid catalyst according to claim 8, it is characterised in that：The size of the porous columnar ceramic is 5 millis Rice × 8 millimeters.
- 10. application of the solid catalyst in vapor phase method synthesizing acrylic ester described in claim 8 or 9.
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Cited By (1)
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| CN112851625A (en) * | 2021-01-21 | 2021-05-28 | 江苏奥克化学有限公司 | Method for preparing cyclic carbonate |
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| CN1424141A (en) * | 2002-12-26 | 2003-06-18 | 中国科学院山西煤炭化学研究所 | Catalyst of synthetic propylene and application thereof |
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