CN105797654B - A kind of ultra high efficiency oxidation reaction apparatus and method preparing cyclohexanone by hexamethylene - Google Patents
A kind of ultra high efficiency oxidation reaction apparatus and method preparing cyclohexanone by hexamethylene Download PDFInfo
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- CN105797654B CN105797654B CN201610309679.1A CN201610309679A CN105797654B CN 105797654 B CN105797654 B CN 105797654B CN 201610309679 A CN201610309679 A CN 201610309679A CN 105797654 B CN105797654 B CN 105797654B
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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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
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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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/082—Controlling processes
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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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/085—Feeding reactive fluids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
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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
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- B01J2208/00539—Pressure
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Abstract
The invention discloses a kind of ultra high efficiency oxidation reaction new process preparing cyclohexanone by hexamethylene, which is made of feed system, 1 main reactor systems of ultra high efficiency tower oxidation reactor R and reaction end gas green treatment system.The cyclohexane oxidation technique is using air as oxide isolation, the high-temperature high-voltage reaction tail gas that is discharged using in oxidation process is as primary heating heat source simultaneously, heat is released into heat exchanger H 1, and by the heat of releasing for heating room temperature hexamethylene raw material, simultaneously using the reaction product of spilling as reheating heat source, the reaction product of spilling enters heat exchanger H 3, heats hexamethylene raw material again.The present invention is compared with traditional tower bubbling oxidation reaction technique or stirring autoclave oxidation reaction technique, reaction efficiency, cyclohexanone yield are improved, ton cyclohexanone product comprehensive energy consumption reduces, and comprehensive production cost reduces, and belongs to the green oxidation reaction process of ultra high efficiency truly.
Description
Technical field
The present invention relates to a kind of device and methods of oxidizing ethyle alkyl, and in particular to a kind of to prepare cyclohexanone by hexamethylene
Ultra high efficiency oxidation reaction apparatus and method.
Background technology
Cyclohexanone is important Organic Chemicals, is synthesis of caprolactam, adipic acid and medicine, coating, dyestuff etc.
The important intermediate of fine chemicals, but also be the original for producing fragrance, rubber antiager, fruit mould inhibitor phenylphenol etc.
Material, it is also possible to make the auxiliary agent of fine chemical product, in addition also have prodigious effect in terms of printing the recycling with plastics.Synthetic fibers
The monomer caprolactam and adipic acid of nylon-6 and nylon -66 are mainly to be produced as raw material using cyclohexanone.Current industrial ring
The technique generally existing efficiency of hexane oxidation preparing cyclohexanone is low and the high problem of energy and material consumption.Traditional cyclohexane oxidation
Operation temperature is 160-165 DEG C, and operation pressure is about 1.2MPa or so.The reaction process not only low cyclohexane conversion rate (3-
5%), the reaction time is long, high energy consumption, but also the disadvantage more than there are cyclohexanone selectivities poor, generation by-product.Therefore, it sends out
Open up ultra high efficiency, low energy consumption, low material consumption cyclohexane oxidation new process be the only way of cyclohexanone manufacturing technology.
Invention content
To solve the defect that existing cyclohexane oxidation prepares cyclohexanone reaction process, the present invention provides one kind by hexamethylene system
The device and method of the ultra high efficiency oxidation reaction of standby cyclohexanone.The present invention is it is critical that devise ultra high efficiency oxidation reactor
R-1 and reaction end gas green handle new system.
An object of the present invention is to provide a kind of ultra high efficiency oxidation reaction apparatus preparing cyclohexanone by hexamethylene, including
Hexamethylene pans C-1, compressor C-2, gas-liquid separation-surge tank C-3, freeze tail gas washing tower C-4, surge tank C-5, superelevation
Imitate tower oxidation reactor R-1, self-priming ultra-fine bubble breaker S-1, First Heat Exchanger H-1, the second heat exchanger H-2, third
Heat exchanger H-3, cryogenic separator CS-1, pump and pipeline, the hexamethylene pans C-1 are equipped with the second pipeline of catalyst inlet
2, the hexamethylene bottoms pans C-1 are connected with the ultra high efficiency tower oxidation lower parts reactor R-1 by the 6th pipeline 6；The superelevation
Effect tower oxidation reactor R-1 top exits pass through the tenth pipeline 10, the 11st pipeline 11 with the refrigeration lower parts tail gas washing tower C-4
Connection, the pipeline are equipped with First Heat Exchanger H-1, and the tops ultra high efficiency tower oxidation reactor R-1 go out equipped with liquid-phase reaction product
Mouthful, which is connected with surge tank C-5, and surge tank C-5 outlet at bottom is connect with third heat exchanger H-3, top and ultra high efficiency tower
The tenth pipeline 10 of formula oxidation reactor R-1 top exits is connected；The first pipeline of cyclohexane feed 1 passes sequentially through refrigeration washing tail gas
The First Heat Exchanger H-1 of tower connection and the third heat exchanger H-3 of surge tank C-5 connections are finally connected with hexamethylene pans C-1；
The refrigeration bottoms tail gas washing tower C-4 are connected with hexamethylene pans C-1, and top is connected with cryogenic separator CS-1, described
The bottoms cryogenic separator CS-1 are connected with the tops refrigeration tail gas washing tower C-4；Inside the ultra high efficiency tower oxidation reactor R-1
Provided with a self-priming ultra-fine bubble breaker S-1, self-priming ultra-fine bubble breaker S-1 passes through the 5th pipeline 5 and gas-liquid
It is connected at the top of separation-surge tank C-3, the 4th pipeline 4 of air intlet, air intlet is connected on the gas-liquid separation-surge tank C-3
Compressor C-2 is provided on pipeline.
In the ultra high efficiency tower oxidation reactor R-1, self-priming ultra-fine bubble breaker S-1 and N block gas are installed
Liquid is distributed baffle T-1 ..., T-N, which is arranged ultra high efficiency tower oxidation reactor R-1's
Lower part and the top for being located at distributor, are fixed on gas-liquid baffle, and baffle is fixed with tower wall, and percent opening is that tower section accumulates
8-16%, there is between every two layers of gas-liquid baffle cycle liquid phase to be inputted from the tangential direction of tower wall, into the tower oxygen of ultra high efficiency
Change reactor R-1；The liquid circulation second that self-priming ultra-fine bubble breaker S-1 is mounted on by one on the outside of reactor R-1 pumps
P-2 provides liquid stream cycle, and the pipeline by connecting between reactor tower body R-1 and S-1 forms pipeline loop, thereon series connection peace
Fill the heat such as heat exchanger, control valve, flowmeter, matter regulates and controls component.In the gas liquid outlet of self-priming ultra-fine bubble breaker S-1
End, it is ultra-fine bubble cutter made of 100nm-500 μm of porous material to be equipped with aperture, which is by stainless steel
(titanium, Zirconium materials, steel alloy, high Ni-based stainless steel etc.), industrial ceramics or other high-strength high temperature-resistant resistant materials are made.From
The ultra-fine bubble breaker S-1 of suction has the function of gas from gentle two kinds of the bubble super fine crushing of sucking.Pass through self-priming ultra-fine bubble
The gas of destroyer S-1, bubble are fractured into ultramicro air bubble (bubble size distribution substantially 300nm-600 μm between), enter
Reactor R-1 is reacted bottom, this makes the few then several times of phase contact area increase of gas-liquid two-phase in reactor, at most tens of
Again or even more than hundreds of times, gas-liquid mass transfer area and gas-liquid mass transfer rate are greatlyd improve, macroscopic view so as to unconventional is improved
Reaction speed.
Specifically, cycle liquid-phase outlet, the 7th pipeline 7 of exit are equipped in the middle part of ultra high efficiency tower oxidation reactor R-1
Be equipped with the second pump P-2, the second condenser F-2 and the second heat exchanger H-2, and with the cycle on ultra high efficiency tower oxidation reactor
Liquid phase entrance is connected, and one of cycle liquid phase entrance is connected with self-priming ultra-fine bubble breaker S-1；The ultra high efficiency is tower
The bottoms oxidation reactor R-1 are additionally provided with equipped with the 8th pipeline 8 for emptying valve.
On the 6th pipeline 6 that the bottoms hexamethylene pans C-1 are connect with the lower parts ultra high efficiency tower oxidation reactor R-1
It is additionally provided with the first pump P-1, the first condenser F-1 and static mixer M-1.
Device of the present invention handles new system comprising reaction end gas green simultaneously, it is by a self-control refrigeration washing tail gas
Tower C-4 and a cryogenic separator CS-1 composition, deep purifying and energy regenerating are carried out to reaction end gas.The self-control refrigeration tail
Gas wash tower C-4 is to be freezed using the energy for the high temperature and pressure tail gas being discharged at the top of reactor R-1, then in refrigeration tail gas
The organic matter that cooled exhaust gas itself is carried secretly in scrubbing tower C-4, including raw material (hexamethylene) and a small amount of product cyclohexanone, cyclohexanol
Deng making them condense and be collected in refrigeration tail gas washing tower C-4 bottoms, then pumping P-3 by conveying third again send to ring
Hexane pans C-1 enters reaction cycle again.Its principles of science is：The high temperature and pressure tail gas being discharged at the top of reactor R-1 has
Higher energy (155-160 DEG C, 1.0MPa or so) preheats hexamethylene raw material by First Heat Exchanger H-1 first, makes tail gas temperature
Degree declines.Tail gas (about 100 DEG C or so, 0.5-0.8MPa) after cooling decompression is by the 11st pipeline 11 by entering through pressure reducing valve
Freeze tail gas washing tower C-4, and wherein, drastically swelling heat absorption makes rapid drop in temperature in scrubbing tower C-4 to tail gas, and temperature can in tower
It can be down to 20-30 DEG C, pressure is down to 0.11-0.12MPa at this point, the organic matter carried secretly in tail gas, wherein most are raw material (ring
Hexane) and a small amount of product cyclohexanone, cyclohexanol etc., it is condensed in the filler of refrigeration tail gas washing tower C-4 and is obtained in bottom of tower
To collection, to which the pressure energy contained by tail gas is fully used.Hereafter, the tail gas of essentially normal temperature and pressure enters back into deep cooling
Separator CS-1, in cryogenic separator CS-1, tail gas detaches under -5 DEG C or so of refrigerant deep cooling again, remaining denier
Organic matter trapped wherein, and collect in the lower part tank of CS-1, it will pass through overflow control mode flow into refrigeration tail
At the top of gas wash tower C-4 packing layers.Finally, almost the reaction air tail gas of cleaning is vented by the 22nd pipeline 22.
The method for preparing cyclohexanone the second object of the present invention is to provide described device, as shown in Fig. 1, it includes three
Main Stage：
In the charging stage, room temperature hexamethylene raw material is heated in First Heat Exchanger H-1 by the reaction end gas of high temperature and pressure first
To 70 DEG C or so, the liquid phase that is then gone out by 24 overflow of the 24th pipeline by reactor upper side in third heat exchanger H-3
Reaction product continues to be heated to 84-85 DEG C into hexamethylene pans C-1, and catalyst is also added extremely by the second pipeline 2 simultaneously
In hexamethylene pans C-1.P-1 is pumped to specify with the raw material first that the hexamethylene bottoms pans C-1 are connected by third pipeline 3
Flow will heat up after hexamethylene raw material sent to the bottom of ultra high efficiency tower oxidation reactor R-1 by the 6th pipeline 6, the 6th
Self controlling valve, flowmeter and static mixer M-1 are in series on pipeline 6.
At the same time, clean air through compressor C-2 be compressed to 1.2MPa, 120 DEG C or so, then it is slow through gas-liquid separation-
It rushes in tank C-3 after drying, is connected with self-priming ultra-fine bubble breaker S-1 flanges by the 5th pipeline 5.In self-priming ultra-fine gas
Steep in destroyer S-1, air be fractured into ultra-fine bubble enter the bottoms ultra high efficiency tower oxidation reactor R-1 aoxidize it is anti-
It answers.
In the oxidation reaction stage, after hexamethylene is entered with clean air in ultra high efficiency tower oxidation reactor R-1,
Oxidation reaction is carried out under catalyst action, operation temperature is 155-160 DEG C, operation pressure 8-10atm.The ultra high efficiency is tower
The gas-liquid baffle T-1 ... T-N of oxidation reactor R-1 be gas-liquid baffle, percent opening be tower section product 8-16%, every two layers
There is cycle liquid phase to be inputted from the tangential direction of tower wall between gas-liquid baffle, as shown in Fig. 2.Self-priming ultra-fine bubble breaker
S-1 is mounted on the lower half of ultra high efficiency tower oxidation reactor R-1.When raw material continually enters in reactor R-1 and reacts continuous
When progress, the liquid level in ultra high efficiency tower oxidation reactor R-1 will gradually rise therewith, when to reach ultra high efficiency tower oxidation anti-for it
When answering device R-1 upper aqueous phase overfalls, the reaction mixture liquid phase of high temperature will flow into surge tank C- by the 24th pipeline 24
5, at this point, importing the tenth pipeline 10 by the 25th pipeline 25 after partially liq vaporization, liquid phase enters third heat exchanger H-3,
Enter follow-up workshop section finally by the 9th pipeline 9.
In tail gas treatment stage, the temperature by the tail gas of First Heat Exchanger H-1 is 100 DEG C or so, pressure 0.5-
0.8MPa enters refrigeration tail gas washing tower C-4 by pressure reducing valve, expands and absorb heat wherein, make in refrigeration tail gas washing tower C-4
Operation temperature decline rapidly.Period, the organic matter in tail gas are condensed into liquid phase and pass through from the bottoms refrigeration tail gas washing tower C-4
13rd pipeline 13 flows out, and hexamethylene pans C-1 is transmitted back to by third pump P-3.Hereafter, the remaining reaction for having micro-content organism
Tail gas will enter cryogenic separator CS-1 by the 12nd pipeline 12, and remnants organic matters therein will further be condensed, and lead to
It crosses the 19th pipeline 19 and overflows back refrigeration tail gas washing tower C-4.The capture rate of organic matter in tail gas is more than in this stage
99.99% or more.
Further, the method for preparing cyclohexanone using above-mentioned apparatus, specifically comprises the steps of：
Step 1, by the first pipeline 1 into hexamethylene pans C-1 plus hexamethylene, by the second pipeline 2 to hexamethylene
Add catalyst in pans C-1, the liquid phase in hexamethylene pans C-1 is by the first pump P-1 by entering superelevation through the 6th pipeline 6
Imitate the bottoms tower oxidation reactor R-1；
Step 2, by the 4th pipeline 4 by through air delivery compressed compressor C-2 to gas-liquid separation-surge tank C-3,
Air after gas-liquid separation-surge tank C-3 dryings enters the ultra-fine bubble breaker S-1 of suction by the 5th pipeline 5, in self-priming
In the ultra-fine bubble breaker S-1 of formula, air is fractured into ultra-fine bubble and enters the progress of the bottoms ultra high efficiency tower oxidation reactor R-1
Oxidation reaction；
Step 3, when the liquid level in ultra high efficiency tower oxidation reactor R-1 be more than middle part cycle liquid-phase outlet when,
The second pump P-2 is opened, respectively by the 15th pipeline 15, the 16th pipeline 16, the 17th pipeline 17, the 18th pipeline 18 by liquid
Phase circulation conveying to cycle liquid phase entrance enter ultra high efficiency tower oxidation reactor (R-1), the liquid phase in the 14th pipeline 14 into
Enter self-priming ultra-fine bubble breaker S-1, the 15th pipeline 15, the 16th pipeline 16, the 17th pipeline 17 and the 18th pipeline
Liquid phase in 18 enters ultra high efficiency tower oxidation reactor R-1 with tower wall tangential direction；
Step 4, after the pressure in ultra high efficiency tower oxidation reactor R-1 reaches setting value, slowly open tower reaction
Gaseous phase outlet valve at the top of device controls exhaust flow, to maintain operating pressure required in reaction tower, high temperature tail gas with pressure logical
It crosses the tenth pipeline 10 and enters First Heat Exchanger H-1, tail gas is expanded to low-temp low-pressure gas by the pressure reducing valve on the 11st pipeline 11
Body enters refrigeration tail gas washing tower C-4, and the organic phase of condensation pumps P-3 by third and is transmitted back to hexamethylene pans C-1, gas phase into
Enter cryogenic separator CS-1, the remaining organic phase of condensation overflows back refrigeration tail gas washing tower C-4, the remaining organic phase overflow of condensation
Refrigeration tail gas washing tower C-4 is returned, gas phase is almost clean reaction air tail gas at this time, you can emptying；
Step 5, with the progress of oxidation reaction in ultra high efficiency tower oxidation reactor R-1, product is from the tower oxygen of ultra high efficiency
The liquid-phase outlet for changing the tops reactor R-1 overflows, and the high temperature and pressure product of spilling enters surge tank C-5, and gas phase passes through the 20th
Five pipelines 25 import the tenth pipeline 10 at the top of ultra high efficiency tower oxidation reactor R-1, and liquid phase is entered by the 26th pipeline 26
Third heat exchanger H-3, and using the heat reheating hexamethylene raw material of liquid phase itself, liquid product enters follow-up after cooling
Workshop section；
After step 6, whole device parking, the valve that empties of the bottoms ultra high efficiency tower oxidation reactor R-1 is opened, reaction is residual
Stay liquid by the 8th pipeline 8 by the second pump P-2 extractions.
The First Heat Exchanger H-1 utilizes the heat hexamethylene raw material of high temperature and pressure tail gas itself.
The third heat exchanger H-3 utilizes the heat reheating hexamethylene raw material for overflowing liquid product itself.
It is realized in the tail gas washing tower C-4 and cryogenic separator CS-1 that freezes by pressure reducing valve using the pressure energy of tail gas
(deep cooling) trapping is condensed to the organic matter carried secretly in tail gas.
First Heat Exchanger H-1 is former using the heat hexamethylene of high temperature and pressure tail gas itself in above-mentioned reaction new process
Material.
Third heat exchanger H-3 is to utilize the heat reheating hexamethylene for overflowing liquid product itself in above-mentioned reaction new process
Alkane raw material.
The purification of reaction end gas in above-mentioned reaction new process is to utilize refrigeration tail gas washing tower C-4 and cryogenic separator
CS-1 is condensed (deep cooling) trapping to realize the recycling refrigeration of reaction end gas pressure energy to the organic matter carried secretly in tail gas,
To realize the multi-efficiency of clean tail gas, raising efficiency object effect and environmental protection.
The present invention is compared to the industrial high energy consumption generally used at present, the hexamethylene alcoxyl of high material-consumption, low rate, low yield
Change preparing cyclohexanone technique, there are following outstanding advantages：
(1) reaction efficiency improves 120-300%；
(2) yield of cyclohexanone improves 8% or more；
(3) ton cyclohexanone product comprehensive energy consumption reduces by 30% or more, and comprehensive production cost reduces by 12% or more；(4) it is one
It is a super
Efficient green oxidation reaction process.
Description of the drawings
Fig. 1 is a kind of ultra high efficiency oxidation reaction new technological flow schematic diagram preparing cyclohexanone by hexamethylene.Wherein：C-1
For hexamethylene pans, C-2 is compressor, and C-3 is gas-liquid separation-surge tank, C-4 is refrigeration tail gas washing tower, and CS-1 is deep
Cold separator, F-1 is the first condenser, F-2 is the second condenser, and H-1 is First Heat Exchanger, H-2 is the second heat exchanger, H-3
For third heat exchanger, M-1 is static mixer, and P-1 is the first pump, P-2 is the second pump, P-3 is third pump, and R-1 is ultra high efficiency
Tower oxidation reactor, S-1 are self-priming ultra-fine bubble breaker, and 1 is the first pipeline, and 2 be the second pipeline, and 3 be third pipeline,
4 be the 4th pipeline, and 5 be the 5th pipeline, and 6 be the 6th pipeline, and 7 be the 7th pipeline, and 8 be the 8th pipeline, and 9 be the 9th pipeline, and 10 are
Tenth pipeline, 11 be the 11st pipeline, and 12 be the 12nd pipeline, and 13 be the 13rd pipeline, and 14 be the 14th pipeline, and 15 be the tenth
Five pipelines, 16 be the 16th pipeline, and 17 be the 17th pipeline, and 18 be the 18th pipeline, and 19 be the 19th pipeline, and 20 be the 20th
Pipeline, 21 be the 21st pipeline, and 22 be the 22nd pipeline, and 23 be the 23rd pipeline, and 24 be the 24th pipeline, and 25 are
25th pipeline, 26 be the 26th pipeline.
Fig. 2 is the schematic cross-section of ultra high efficiency tower oxidation reactor R-1 circulating liquids flow direction.
Specific implementation mode
Embodiment 1：
The tower diameter of ultra high efficiency tower oxidation reactor R-1 is 800mm, tower height 4.5m, shares five layers of gas-liquid baffle, gas-liquid
Baffle percent opening is 10%, and self-priming ultra-fine bubble breaker S-1 is fixed on first layer gas-liquid baffle center, self-priming ultra-fine
The lower part gas liquid outlet end of bubble breaker S-1, it is ultra-fine bubble cutter made of 100 μm of porous materials to be equipped with aperture,
Plate spacing between gas-liquid baffle is 0.4m, there is a cycle liquid-phase outlet below first layer gas-liquid baffle.Start rank in reaction
Section, the hexamethylene raw material of 100kg/h is passed through into the first pipeline 1, and cyclohexene raw material passes through cyclohexene pans C-1 and catalyst
Mixing is delivered in static mixer M-1 by the first pump P-1 by third pipeline 3 and is sufficiently mixed, then passes through the 6th pipeline 6
Into the bottom of ultra high efficiency tower oxidation reactor R-1, temperature is passed through into gas-liquid separation-surge tank C-3 by compressor C-2
The air for being 5atm for 120 DEG C, pressure, air after drying enter the ultra-fine bubble breaker S- of self-priming by the 5th pipeline 5
1, air is made into super broken bubble and enters the bottoms ultra high efficiency tower oxidation reactor R-1 progress oxidation reaction, when ultra high efficiency is tower
When liquid level in oxidation reactor R-1 is more than cycle liquid-phase outlet, open the second pump P-2, liquid phase by the 7th pipeline 7 by
Second pump P-2 is respectively delivered to the ultra-fine bubble breaker S-1 of self-priming and liquid phase circulation entrance, wherein cycle liquid phase is with tower wall tangent line
Direction enters in tower.The operation temperature of ultra high efficiency tower oxidation reactor R-1 is set as 140 DEG C, pressure 6atm, works as ultra high efficiency
After pressure in tower oxidation reactor R-1 reaches setting value, slowly open at the top of ultra high efficiency tower oxidation reactor R-1
Gaseous phase outlet valve, control exhaust flow are 12m3/ h, to maintain the operating pressure in ultra high efficiency tower oxidation reactor R-1,
The tail gas of high temperature and pressure reaches First Heat Exchanger H-1, hexamethylene raw material is heated to 100 DEG C, tail gas passes through the 11st pipeline 11
Entering refrigeration tail gas washing tower C-4 after being depressurized by pressure reducing valve, drastically swelling heat absorption makes rapid drop in temperature in tower to tail gas in tower,
Temperature is down to 25 DEG C in tower, and organic matter is condensed into liquid phase and is transmitted back to hexamethylene pans C-1, normal temperature and pressure by third pump P-3
The a little remaining organic matter of tail gas entrainment enter cryogenic separator CS-1, tail gas detaches under -5 DEG C of refrigerant deep cooling again,
Remaining denier organic matter is condensed into liquid phase and overflows back refrigeration tail gas washing tower C-4, air discharge.When ultra high efficiency tower oxidation
Liquid level in reactor R-1 opens the valve of overfall, the product of spilling passes through the 24th pipeline more than after overfall
24 enter surge tank C-5, and the gas phase of reduction vaporization imports the tenth pipeline 10 by the 25th pipeline 25, and liquid phase enters third and changes
Hexamethylene is heated to 120 DEG C by hot device H-3 reheating raw materials, and subsequent product enters follow-up work by the 26th pipeline 26
Section.The capture rate of organic matter reaches 99.9% or more in final tail gas, and tail gas and product pressure can reach with the utilization rate of heat
80%.
Embodiment 2
The tower diameter of ultra high efficiency tower oxidation reactor R-1 is 800mm, tower height 4.5m, shares five layers of gas-liquid baffle, gas-liquid
Baffle percent opening is 10%, and self-priming ultra-fine bubble breaker S-1 is fixed on first layer gas-liquid baffle center, self-priming ultra-fine
The lower part gas liquid outlet end of bubble breaker S-1, it is ultra-fine bubble cutter made of 100 μm of porous materials to be equipped with aperture,
Plate spacing between gas-liquid baffle is 0.4m, there is a cycle liquid-phase outlet below first layer gas-liquid baffle.Start rank in reaction
Section, the hexamethylene raw material of 150kg/h is passed through into the first pipeline 1, and cyclohexene raw material passes through cyclohexene pans C-1 and catalyst
Mixing is delivered in static mixer M-1 by the first pump P-1 by third pipeline 3 and is sufficiently mixed, then passes through the 6th pipeline 6
Into the bottom of ultra high efficiency tower oxidation reactor R-1, temperature is passed through into gas-liquid separation-surge tank C-3 by compressor C-2
The air for being 5atm for 120 DEG C, pressure, air after drying enter the ultra-fine bubble breaker S- of self-priming by the 5th pipeline 5
1, air is made into super broken bubble and enters the bottoms ultra high efficiency tower oxidation reactor R-1 progress oxidation reaction, when ultra high efficiency is tower
When liquid level in oxidation reactor R-1 is more than cycle liquid-phase outlet, open the second pump P-2, liquid phase by the 7th pipeline 7 by
Second pump P-2 is respectively delivered to the ultra-fine bubble breaker S-1 of self-priming and liquid phase circulation entrance, wherein cycle liquid phase is with tower wall tangent line
Direction enters in tower.The operation temperature of ultra high efficiency tower oxidation reactor R-1 is set as 160 DEG C, pressure 7atm, works as ultra high efficiency
After pressure in tower oxidation reactor R-1 reaches setting value, slowly open at the top of ultra high efficiency tower oxidation reactor R-1
Gaseous phase outlet valve, control exhaust flow are 18m3/ h, to maintain the operating pressure in ultra high efficiency tower oxidation reactor R-1,
The tail gas of high temperature and pressure reaches First Heat Exchanger H-1, hexamethylene raw material is heated to 110 DEG C, tail gas passes through the 11st pipeline 11
Entering refrigeration tail gas washing tower C-4 after being depressurized by pressure reducing valve, drastically swelling heat absorption makes rapid drop in temperature in tower to tail gas in tower,
Temperature is down to 25 DEG C in tower, and organic matter is condensed into liquid phase and is transmitted back to hexamethylene pans C-1, normal temperature and pressure by third pump P-3
The a little remaining organic matter of tail gas entrainment enter cryogenic separator CS-1, tail gas detaches under -5 DEG C of refrigerant deep cooling again,
Remaining denier organic matter is condensed into liquid phase and overflows back refrigeration tail gas washing tower C-4, air discharge.When ultra high efficiency tower oxidation
Liquid level in reactor R-1 opens the valve of overfall, the product of spilling passes through the 24th pipeline more than after overfall
24 enter surge tank C-5, and the gas phase of reduction vaporization imports the tenth pipeline 10 by the 25th pipeline 25, and liquid phase enters third and changes
Hexamethylene is heated to 125 DEG C by hot device H-3 reheating raw materials, and subsequent product enters follow-up work by the 26th pipeline 26
Section.The capture rate of organic matter reaches 99.9% or more in final tail gas, and tail gas and product pressure can reach with the utilization rate of heat
75%.
Claims (7)
1. a kind of ultra high efficiency oxidation reaction apparatus preparing cyclohexanone by hexamethylene, which is characterized in that including hexamethylene pans
（C-1）, compressor（C-2）, gas-liquid separation-surge tank（C-3）, freeze tail gas washing tower（C-4）, surge tank（C-5）, ultra high efficiency
Tower oxidation reactor（R-1）, self-priming ultra-fine bubble breaker（S-1）, First Heat Exchanger（H-1）, the second heat exchanger（H-
2）, third heat exchanger（H-3）, cryogenic separator（CS-1）, pump and pipeline, the hexamethylene pans（C-1）It is equipped with catalysis
The second pipeline of agent import（2）, hexamethylene pans（C-1）Bottom and ultra high efficiency tower oxidation reactor（R-1）Lower part passes through
Six pipelines（6）It is connected；The ultra high efficiency tower oxidation reactor（R-1）Top exit and refrigeration tail gas washing tower（C-4）Lower part
Pass through the tenth pipeline（10）, the 11st pipeline（11）Connection is equipped with First Heat Exchanger between the tenth pipeline and the 11st pipeline（H-
1）, ultra high efficiency tower oxidation reactor（R-1）Top is exported equipped with liquid-phase reaction product, the outlet and surge tank（C-5）It is connected,
Surge tank（C-5）Outlet at bottom and third heat exchanger（H-3）Connection, top and ultra high efficiency tower oxidation reactor（R-1）Top
Export the tenth pipeline（10）It is connected；The first pipeline of cyclohexane feed（1）Pass sequentially through refrigeration tail gas washing tower connection first is changed
Hot device（H-1）And surge tank（C-5）The third heat exchanger of connection（H-3）Finally with hexamethylene pans（C-1）It is connected；The system
Cold tail gas washing tower（C-4）Bottom and hexamethylene pans（C-1）It is connected, top and cryogenic separator（CS-1）It is connected, it is described
Cryogenic separator（CS-1）Bottom and refrigeration tail gas washing tower（C-4）Top is connected；The self-priming ultra-fine bubble breaker（S-
1）Positioned at ultra high efficiency tower oxidation reactor（R-1）Lower inside, the self-priming ultra-fine bubble breaker（S-1）Pass through the 5th
Pipeline（5）With gas-liquid separation-surge tank（C-3）Top connects, the gas-liquid separation-surge tank（C-3）On be connected with air intlet
4th pipeline（4）, compressor is provided on air intlet pipeline（C-2）；
The ultra high efficiency tower oxidation reactor（R-1）It is internally provided with distributor and gas-liquid distribution baffle, it is described self-priming super
Thin bubble breaker（S-1）It is arranged in the top of distributor, is fixed on gas-liquid distribution baffle, in self-priming ultra-fine bubble breaking
Device（S-1）Gas liquid outlet end ultra-fine bubble cutter is installed；
The ultra high efficiency tower oxidation reactor（R-1）On every two layers of gas-liquid baffle all there are one recycle liquid phase entrance, liquid phase with
Tower wall tangential direction enters ultra high efficiency tower oxidation reactor（R-1）.
2. a kind of ultra high efficiency oxidation reaction apparatus preparing cyclohexanone by hexamethylene according to claim 1, feature exist
In ultra high efficiency tower oxidation reactor in described device（R-1）Middle part is equipped with cycle liquid-phase outlet, the 7th pipeline of exit
（7）It is equipped with the second pump（P-2）, the second condenser（F-2）With the second heat exchanger（H-2）, and reacted with ultra high efficiency tower oxidation
Cycle liquid phase entrance on device is connected, one of cycle liquid phase entrance and self-priming ultra-fine bubble breaker（S-1）It is connected；Institute
State ultra high efficiency tower oxidation reactor（R-1）Bottom is additionally provided with equipped with the 8th pipeline for emptying valve（8）.
3. a kind of ultra high efficiency oxidation reaction apparatus preparing cyclohexanone by hexamethylene according to claim 1, feature exist
In described device cyclohexane pans（C-1）Bottom and ultra high efficiency tower oxidation reactor（R-1）6th pipe of lower part connection
Road（6）On be additionally provided with the first pump（P-1）, the first condenser（F-1）And static mixer（M-1）.
4. a kind of method for the ultra high efficiency oxidation reaction preparing cyclohexanone by hexamethylene using device described in claim 1,
It is characterized in that, comprises the steps of：
Step 1 passes through the first pipeline（1）To hexamethylene pans（C-1）In plus hexamethylene, pass through the second pipeline（2）To hexamethylene
Alkane pans（C-1）In plus catalyst, hexamethylene pans（C-1）In liquid phase pass through first pump（P-1）By through the 6th pipeline
（6）Into ultra high efficiency tower oxidation reactor（R-1）Bottom；
Step 2 passes through the 4th pipeline（4）It will be through compressor（C-2）Compressed air delivery is to gas-liquid separation-surge tank（C-
3）, through gas-liquid separation-surge tank（C-3）Air after drying passes through the 5th pipeline（5）Into the ultra-fine bubble breaker of suction（S-
1）, in self-priming ultra-fine bubble breaker（S-1）Interior, air is fractured into ultra-fine bubble and enters ultra high efficiency tower oxidation reactor
（R-1）Bottom carries out oxidation reaction；
Step 3, when ultra high efficiency tower oxidation reactor（R-1）In liquid level be more than middle part cycle liquid-phase outlet when, beat
Open the second pump（P-2）, liquid phase circulation is delivered to cycle liquid phase entrance respectively and enters ultra high efficiency tower oxidation reactor（R-1）With
Self-priming ultra-fine bubble breaker（S-1）, liquid phase enters ultra high efficiency tower oxidation reactor with tower wall tangential direction（R-1）；
Step 4, when ultra high efficiency tower oxidation reactor（R-1）In pressure reach setting value after, slowly open tower reactor
The gaseous phase outlet valve at top, high temperature tail gas with pressure pass through the tenth pipeline（10）Into First Heat Exchanger（H-1）, tail gas passes through
11 pipelines（11）On pressure reducing valve be expanded to low temperature low pressure gas and enter refrigeration tail gas washing tower（C-4）, the organic phase of condensation
It is pumped by third（P-3）It is transmitted back to hexamethylene pans（C-1）, gas phase enters cryogenic separator（CS-1）, the remnants of condensation have
Machine mutually overflows back refrigeration tail gas washing tower（C-4）；
Step 5, with ultra high efficiency tower oxidation reactor（R-1）The progress of middle oxidation reaction, product is from ultra high efficiency tower oxidation
Reactor（R-1）The liquid-phase outlet on top overflows, and the high temperature and pressure product of spilling enters surge tank（C-5）, gas phase passes through second
15 pipelines（25）Import ultra high efficiency tower oxidation reactor（R-1）The tenth pipeline of top（10）, liquid phase pass through the 26th pipe
Road（26）Into third heat exchanger（H-3）, and using the heat reheating hexamethylene raw material of liquid phase itself, liquid product is through cold
But enter follow-up workshop section afterwards；
After step 6, whole device parking, ultra high efficiency tower oxidation reactor is opened（R-1）Bottom empties valve, reaction residual
Liquid passes through the 8th pipeline（8）By the second pump（P-2）Extraction.
5. according to the method described in claim 4, it is characterized in that, the First Heat Exchanger（H-1）Utilize high temperature and pressure tail gas
The heat hexamethylene raw material of itself.
6. according to the method described in claim 4, it is characterized in that, the third heat exchanger（H-3）Utilize spilling liquid product
The heat reheating hexamethylene raw material of itself.
7. according to the method described in claim 4, it is characterized in that, using tail gas pressure energy, by pressure reducing valve, in refrigeration tail
Gas wash tower（C-4）And cryogenic separator（CS-1）Middle realize carries out condensing trapping to the organic matter carried secretly in tail gas.
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