CN105967984A - Method and system for producing cyclohexanone with phenol - Google Patents
Method and system for producing cyclohexanone with phenol Download PDFInfo
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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
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- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention discloses a method and system for producing cyclohexanone with phenol. The method is characterized by comprising the following steps that the raw material phenol is heated through a phenol preheater and then sent to a phenol vaporizer, mixed gas of the phenol and decarburized hydrogen is sent to a raw material superheater and sent to a hydrogenation reactor after superheating is conducted, in the hydrogenation reactor, hydrogen is added to the phenol to generate the cyclohexanone, a hydrogenation reaction product is sent to a hydrogenation reactor heat recovery heat exchanger for heat recovery and then sent to a dehydrogenation tower, hydrogen which does not react is separated, and a crude cyclohexanone product is obtained at the bottom of the dehydrogenation tower. The system comprises the phenol preheater, the phenol vaporizer, the raw material superheater, a hydrogen preheater, a hydrogen heater, the hydrogenation reactor, the hydrogenation reactor heat recovery heat exchanger, a decarburization reactor and the dehydrogenation tower. The system and method have the advantages that high-efficiency and high-selectivity hydrogenation preparation of the cyclohexanone with the phenol is achieved, the technological process is simple, and the product cyclohexanone is high in yield.
Description
Technical field
The present invention relates to a kind of cyclohexanone production process, especially relate to a kind of method of phenol production Ketohexamethylene and be
System.
Background technology
Ketohexamethylene is a kind of application industrial chemicals widely, plays an important role in commercial production, daily life.
By its purposes, Ketohexamethylene is divided into amide to use and non-amide two big classes, and wherein 70% is amide Ketohexamethylene.Conventional nylon 6 He
Nylon66 fiber Ketohexamethylene is prepared.Further, since Ketohexamethylene has the feature of highly dissoluble and low volatility, can make
Use for organic solvent, the most non-amide Ketohexamethylene.For nitrocotton, cellulose, nitrocellulose, polyurethane, chloroethylene polymerization
The polymer such as thing and copolymer is a kind of preferably solvent；Ketohexamethylene is used in mixed way with other solvents, adjustable systems evaporation speed
Degree；In leather industry, Ketohexamethylene can do degreasing agent and detergent, is used for cleaning reactor；It addition, Ketohexamethylene is led at medicine
The aspect such as territory, antiaging agent is also widely used；Such as, special Maron, cough U.S.A the pharmaceutical intermediate such as to cut be by Ketohexamethylene and cyanogen
Acetic acidreaction, prepares after treatment.
At present, the industrial process of Ketohexamethylene mainly has three kinds: cyclohexane oxidation process, cyclohexene hydration method and phenol add
Hydrogen method.
Within a very long time, cyclohexane oxidation process is main production method.The feature of cyclohexane oxidation process is: for
Improving the safety of oxidation reaction and obtain high selectivity, a conversion ratio of hexamethylene is normally controlled in 4-5wt%, this band
The negative consequence come is that a large amount of unreacted benzene feedstock needs a large amount of cycling and reutilizations, and this is accomplished by consuming substantial amounts of energy, from
And make this process energy consumption the highest, and with the presence of explosive mixture in course of reaction, System risk is high.
Cyclohexene hydration method is a kind of more advanced cyclohexanone production process occurred after cyclohexane oxidation process.Cyclohexene
The feature of hydration method is: when producing intermediate product cyclohexene, owing to hexamethylene is more more stable than cyclohexene, and therefore hexamethylene hydrogenation is raw
During producing cyclohexene, can the substantial amounts of hexamethylene of by-product.And produce final products Ketohexamethylene, also need through cyclohexene water
Hexalin, cyclohexanol dehydrogenation operation are produced in symphysis, and technological process is long, and energy consumption is high, and equipment is many, and investment is big.And use this technique raw
The Ketohexamethylene produced is the longest due to flow process, and in the Ketohexamethylene that final production goes out, impurity composition is many, thus causes cyclohexene hydration method
When the Ketohexamethylene produced is used for producing caprolactam, the caprolactam impurity content produced is many, is generally not used to produce height
End spinning.
Phenol hydrogenation method is the another kind of important method producing Ketohexamethylene, its technological principle and cyclohexane oxidation process and hexamethylene
Alkene hydration method is the most different, and owing to there is oxygen on its phenyl ring, therefore it can obtain Ketohexamethylene by hydrogenation reaction one step.Produce
Technique is simple, and flow process is the shortest, and the Ketohexamethylene quality that this technique produces is good, and impurity content is low, is widely used in the high-end downstream of production
Product.But, phenol hydrogenation reaction hydrogenation difficulty, side reaction difficulty controls, and how to improve hydrogenation efficiency, improves target product Ketohexamethylene
Yield be phenol hydrogenation produce Ketohexamethylene technology a difficult problem.
It is as follows that phenol hydrogenation produces Ketohexamethylene fundamental reaction principle:
The most effectively realizing first step reaction activation, can second step hydrogenation reaction occurs be the key that realize this technology.And,
During preparing cyclohexanone from phenol, often produce Hexalin by-product.The most effectively reduce by-product, realize height
Efficiency, high selective phenol hydrogenation prepare the key that Ketohexamethylene is technology.
Summary of the invention
The technical problem to be solved is to provide one, and flow process is simple, raw material availability is high, target product hexamethylene
The method and system of the phenol production Ketohexamethylene that ketone yield is high, Ketohexamethylene impurity content is few.
The present invention solves the technical scheme that above-mentioned technical problem used: a kind of method of phenol production Ketohexamethylene, bag
Include following steps:
(1) raw material phenol is sent into after phenol preheater is heated to 120-140 DEG C phenol carburator, in phenol carburator,
Controlling phenol carburator top pressure is 0.2-0.25MPaG, and phenol is heated dual function, benzene by decarburization hydrogen partial pressure and steam
Phenol is vaporized into gas and decarburization hydrogen is mixed and sends into raw material superheater, by phenol and decarburization hydrogen group in raw material superheater
Hydrogenation reactor sent into by the admixture of gas become after being superheated to 175-195 DEG C of activation, and controls to enter the gas of hydrogenation reactor
In body mixture, phenol is 1:2-1:6 with the mol ratio of hydrogen；
(2) controlling the reaction temperature of hydrogenation reactor for 180-195 DEG C, Stress control is 0.1-0.2MPaG, anti-at hydrogenation
In answering device, phenol hydrogenation generates Ketohexamethylene, and with generating by-product cyclic hexanol；Wherein hydrogenation reactor is calandria type fixed bed
Isothermal reactor, calandria type fixed bed isothermal reactor is built with Al2O3Pd catalyst for carrier；
(3) hydrogenation reaction product is sent into hydrogenation reactor heat recovering heat exchanger bottom hydrogenation reactor, in hydrogenation reaction
In device heat recovering heat exchanger, hydrogenation reaction product and decarburization hydrogen carry out heat exchange, and the decarburization hydrogen after intensification sends into phenol vaporization
Device, the hydrogenation reaction product being cooled to 105-115 DEG C sends into dehydrogenation tower；
(4) control to be 0.05-0.15MPaG by the tower top pressure of dehydrogenation tower, hydrogenation reaction product is separated, dehydrogenation tower
Tower top obtains unreacted hydrogen, obtains the Ketohexamethylene crude product that temperature is 95-105 DEG C at the bottom of the tower of dehydrogenation tower.
The preparation technology flow process of the decarburization hydrogen described in step (1) is: be 20-30ppm's by hydrocarbon content
Raw hydrogen is after hydrogen preheater is preheated to 160-170 DEG C, then sends into thermal insulation after hydrogen heater is heated to 230-240 DEG C
Fixed-bed type decarburizing reaction device；The carbon monoxide in raw hydrogen and carbon dioxide, decarburizing reaction is removed in decarburizing reaction device
Use Al2O3For the Ni catalyst of carrier, decarburizing reaction temperature controls as 235-245 DEG C, and Stress control is 1.1-1.3MPaG, de-
Carbon obtains carbon monoxide and the concentration of total carbon dioxide decarburization hydrogen less than 2ppb after processing, decarburization hydrogen is sent into hydrogen preheating
Device, in hydrogen preheater, raw hydrogen and decarburization hydrogen carry out heat exchange, the decarburization hydrogen hydrogenated reactor heat after cooling
Reclaim after heat exchanger heats up and send into phenol carburator.Removal of carbon monoxide, carbon dioxide can avoid Pyrogentisinic Acid's hydrogenation catalyst
Poison.
In step (4), the top gaseous phase of dehydrogenation tower is through gas-liquid separation after the first overhead condenser is cooled to 40 DEG C, separates
After liquid through overhead reflux pumped back dehydrogenation top of tower as backflow, gas is sent into and is reclaimed hydrogen gas compressor and boost in pressure arrived
Dehydrogenation top of tower, gas is sent back to through the second overhead condenser cooling the liquid after gas-liquid separation, separation after 0.2-0.3MPaG
Sending into phenol carburator after the hydrogenated reactor heat recovering heat exchanger heat temperature raising of major part, residue small part discharges system.
The gas flow of above-mentioned discharge system controls the 0.005-0.01 mol% for reclaiming hydrogen total amount, is discharged by control
The gas flow going out system is 1 mol%-4 mol% to maintain the content of the gaseous impurity (methane etc.) entering hydrogenation reactor, from
And maintain effectively carrying out of hydrogenation reaction.Testing discovery through inventor: after methane content is more than 4mol% in hydrogen, hydrogenation is anti-
The selectivity answered significantly reduces, and if in hydrogen to be maintained methane content be consistently lower than 1mol%, system needs discharge a large amount of
Gas could maintain.Through experimental test, the content maintaining the gaseous impurity (methane) entering hydrogenation reactor is 1mol%-
4mol% is optimal.
In the admixture of gas entering hydrogenation reactor described in step (1), hydrogen controls as 5:1-with the mol ratio of nitrogen
2:1.Reasonably nitrogen content, reduces reactor coking and improves target product selectivity.
Described hydrogenation reactor is divided into upper reaction section and bottom cooling section, and described hydrogenation reactor is with boiler feedwater
Send into hydrogenation reactor shell-side and produce the saturated vapor of 0.2-0.3MPaG.In controlling hydrogenation reactor 6, temperature is 190 DEG C.
Bottom cooling section the most quickly reduces upper reaction section hydrogenation products temperature, effectively suppresses the generation of side reaction, and carries simultaneously
High heat organic efficiency.
A kind of system for above-mentioned phenol production Ketohexamethylene method, including phenol preheater, phenol carburator, raw material mistake
Hot device, hydrogen preheater, hydrogen heater, hydrogenation reactor, hydrogenation reactor heat recovering heat exchanger, decarburizing reaction device and dehydrogenation
Tower, described phenol preheater is connected with the sidepiece charging aperture of described phenol carburator, the top of described phenol carburator
Discharging opening is connected with the import of described raw material superheater, the outlet of described raw material superheater and described hydrogenation reactor
Its top feed mouth connects, and the bottom discharge mouth of described hydrogenation reactor enters with described hydrogenation reactor heat recovering heat exchanger
Mouth connects, and the outlet of described hydrogenation reactor heat recovering heat exchanger is connected with the lower end charging aperture of described dehydrogenation tower, described
One end of hydrogen preheater, described hydrogen heater, described decarburizing reaction device and described hydrogen preheater another
End be in turn connected to form closed circuit, described hydrogen preheater by described hydrogenation reactor recuperation of heat reactor with described
The lower end air inlet of phenol carburator connect, the bottom of described dehydrogenation tower is provided with Ketohexamethylene product outlet.
The top gas phase exit of described dehydrogenation tower is provided with the first overhead condenser, the first described overhead condenser
Liquid-phase outlet be connected with the upper end import of described dehydrogenation tower by overhead reflux pump, the gas of the first described overhead condenser
Outlet connects recovery hydrogen gas compressor mutually, and described recovery hydrogen gas compressor connects the second overhead condenser, the second described tower
The liquid-phase outlet of top condenser is connected with the upper end import of described dehydrogenation tower by overhead reflux pump, and the second described tower top is cold
The gaseous phase outlet of condenser is connected with described hydrogenation reactor heat recovering heat exchanger.
Described dehydrogenation tower is plate tower, and column plate can be float valve or sieve plate, and the number of plates is 5-10 layer.Use dehydrogenation tower
Separating hydrogen from hydrogenation products to recycle, after separation, tower base ring hexanone crude product temperature is 95-105 DEG C.Conventional skill
Art is that by whole materials, the gas-liquid mixture that hydrogenation reactor heat recovering heat exchanger is discharged is cooled to 50 DEG C by coolant, then
Carry out gas-liquid separation, obtain temperature and be hydrogen and the Ketohexamethylene crude product of 50 DEG C.And the Ketohexamethylene crude product that the present invention obtains
Temperature is 95-105 DEG C, can significantly reduce subsequent fine fraction from energy consumption, save cold simultaneously, energy-saving effect is notable.
In the cylinder of described phenol carburator and be positioned at the lower horizontal of sidepiece charging aperture of described phenol carburator
Being provided with dismountable tubing heat exchanger, the barrel upper level of described phenol carburator is provided with hydrogen inlet supervisor,
Extending the center in cylinder in described hydrogen inlet supervisor, the end of described hydrogen inlet supervisor connects has four longitudinal directions to set
Putting and equally distributed hydrogen conveying arm, the lower section of described hydrogen conveying arm is provided with a horizontal circle hydrogen and divides
Cloth device, the end of four described hydrogen conveying arms is connected with described circular Hydrogen distribution device respectively, described circular hydrogen
Gas distributor is positioned at the lower section of described tubing heat exchanger, and described circular Hydrogen distribution device includes the interior China and foreign countries being coaxially disposed
3 ring shape Hydrogen distribution pipes, each described annular Hydrogen distribution pipe is provided with several hydrogen dispersion hole.This structure
Make hydrogen and raw material phenol be more fully mixed, and can effectively reduce the vapourizing temperature of phenol.
Compared with prior art, it is an advantage of the current invention that:
(1) controlling to enter the phenol of raw material superheater with the mol ratio of decarburization hydrogen is 1:2-1:6, goes out the material of raw material superheater
Temperature is 175-195 DEG C, effectively achieves the efficient activation of phenol.
(2) controlling to enter the decarburization hydrogen of hydrogenation reactor with the mol ratio of nitrogen is 5:1-2:1.The reasonable concentration of nitrogen
The selectivity of reaction can be improved, increase the life-span of catalyst.
(3) decarburization hydrogen is passed through in phenol carburator liquid, utilizes decarburization hydrogen partial pressure to reduce benzene in phenol carburator
The vapourizing temperature of phenol, in making phenol carburator, phenol vapourizing temperature is reduced to 150-160 DEG C by 180 DEG C.
(4) control raw material superheater outlet temperature and be 175-195 DEG C, thus ensure that the conversion ratio of hydrogenation reaction and yield are equal
The highest.
(5) hydrogenation reactor is calandria type fixed bed reactor, and reactor is divided into upper reaction section and bottom cooling section.Under
Portion's cooling section can quickly reduce hydrogenation products temperature, effectively reduces the generation of side reaction.The most fully reclaim what reaction was released
Heat, can finally control hydrogenation reaction product going out the temperature of hydrogenation reactor is 150 DEG C.
(6) using distillation column to separate hydrogen from hydrogenation products, after separation, to be 95-105 DEG C (normal for Ketohexamethylene crude product temperature
Rule use cooling isolated hydrogenation products temperature be 40-50 DEG C), can significantly reduce subsequent fine fraction from energy consumption, with
Time save cold, energy-saving effect is notable.
(7) by arranging hydrogen decarburizing reaction device, it is ensured that send into the carbon monoxide of hydrogenation reactor, total carbon dioxide content
Less than 2ppb, thus avoid carbon monoxide, carbon dioxide that hydrogenation catalyst is poisoned, improve catalyst service life.
(8) reaction method under the present invention and system finally can realize phenol conversion more than 99 wt %, Ketohexamethylene selection
Rate is more than 90 wt %, and Ketohexamethylene+Hexalin selection rate is more than 99 wt %.
Accompanying drawing explanation
Fig. 1 is the process chart of the method and system of phenol production Ketohexamethylene of the present invention；
Fig. 2 is the structural representation one of phenol carburator of the present invention；
Fig. 3 is the structural representation two of phenol carburator of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Specific embodiment one
A kind of method of phenol production Ketohexamethylene, as it is shown in figure 1, comprise the following steps:
(1) raw material phenol is sent into after phenol preheater 1 is heated to 130 DEG C phenol carburator 2, in phenol carburator 2, control
Phenol carburator 2 top pressure processed is 0.22MPaG, and phenol is heated dual function by decarburization hydrogen partial pressure and steam, and phenol vaporizes
Become gas and decarburization hydrogen to be mixed and send into raw material superheater 3, be made up of phenol and decarburization hydrogen in raw material superheater 3
Admixture of gas sends into hydrogenation reactor 6 after being superheated to 185 DEG C, controls benzene in the admixture of gas of entrance hydrogenation reactor 6
Phenol is 1:5 with the mol ratio of hydrogen；Controlling the mol ratio of hydrogen and nitrogen in the admixture of gas of entrance hydrogenation reactor 6 is 3:
1；
(2) the reaction mass temperature controlling hydrogenation reactor 6 is 190 DEG C, and pressure is 0.15MPaG, benzene in hydrogenation reactor 6
Phenol is hydrogenated to Ketohexamethylene, and hydrogenation reactor 6 is calandria type fixed bed reactor, and calandria type fixed bed reactor is built with Al2O3
Pd catalyst for carrier；
(3) hydrogenation reaction product is sent into hydrogenation reactor heat recovering heat exchanger 7 bottom hydrogenation reactor 6, anti-at hydrogenation
Answering hydrogenation reaction product and decarburization hydrogen in device heat recovering heat exchanger 7 to carry out heat exchange, after heat exchange, the temperature of decarburization hydrogen is 125
DEG C, it is then fed into phenol carburator 2；Hydrogenation reaction product temperature after cooling is 112 DEG C, sends into dehydrogenation tower 9；
(4) control to be 0.12MPaG by the tower top pressure of dehydrogenation tower 9, hydrogenation reaction product is separated, the tower top of dehydrogenation tower 9
Obtain unreacted hydrogen, at the bottom of the tower of dehydrogenation tower 9, obtain the Ketohexamethylene crude product that temperature is 100 DEG C.Wherein dehydrogenation tower 9 is distillation
Tower, uses the hydrogen in distillation column separation hydrogenation reaction product, and after separation, Ketohexamethylene crude product temperature is 100 DEG C.Ketohexamethylene is thick
Product temperatur is high, can reduce subsequent fine fraction from energy consumption, save cold simultaneously, energy-saving effect is notable.
In this particular embodiment, the preparation flow of decarburization hydrogen is: be the feed hydrogen of 25ppm by hydrocarbon content
Gas, after hydrogen preheater 4 is preheated to 165 DEG C, brings up to 235 DEG C through hydrogen heater 5 temperature, is then fed into insulation fix bed
Formula decarburizing reaction device 8, in decarburizing reaction device 8, decarburizing reaction uses Al2O3For the Ni catalyst of carrier, reaction temperature 240 DEG C,
Stress control is 1.2MPaG, obtains carbon monoxide and the concentration of total carbon dioxide decarburization hydrogen less than 2ppb after carbonization treatment, will
Decarburization hydrogen sends into hydrogen preheater 4, and in hydrogen preheater 4, raw hydrogen and decarburization hydrogen carry out heat exchange, temperature after cooling
Degree be 115 DEG C of decarburization hydrogen with from the second overhead condenser 14 reclaim hydrogen and supplementary nitrogen together with send into hydrogenation reaction
Device heat recovering heat exchanger 7, sends into phenol carburator 2 after intensification.
In above-mentioned steps (4), the top gaseous phase of dehydrogenation tower 9 divides through gas-liquid after the first overhead condenser 11 is cooled to 40 DEG C
From, the liquid after separation delivers to dehydrogenation tower 9 overhead reflux through overhead reflux pump 12, and gas is sent into and reclaimed hydrogen gas compressor 13 by pressure
Power is cooled to 40 DEG C and liquid after gas-liquid separation, separation is sent back to de-through the second overhead condenser 14 after rising to 0.25MPaG
Hydrogen tower 9 top, the second overhead condenser 14 top effluent air major part hydrogenated reactor heat recovering heat exchanger 7 heating rises
Temperature sends into phenol carburator 2 after 125 DEG C, and residue partial gas discharges system.Control the gas flow of discharge system for reclaiming
0.008 mol% of hydrogen total amount.The gas flow of system is given off miscellaneous with the gas controlling to enter hydrogenation reactor 6 by control
The content of matter methane is 3mol%, thus ensures efficiently carrying out of hydrogenation reaction.Hydrogenation reactor 6 be divided into upper reaction section and under
Portion's cooling section, hydrogenation reactor 6 is sent into hydrogenation reactor 6 shell-side with boiler feedwater and is produced the saturated vapor use of 0.2-0.3MPaG
In controlling hydrogenation reactor 6, temperature is 190 DEG C.
In this particular embodiment, as shown in Figures 2 and 3, the cylinder of phenol carburator 2 is interior and is positioned at phenol carburator 2
The lower horizontal of sidepiece charging aperture 15 be provided with dismountable tubing heat exchanger 16, the barrel upper water of phenol carburator 2
The flat hydrogen inlet that is provided with is responsible for 17, extends the center in phenol carburator 2 cylinder, hydrogen inlet master in hydrogen inlet supervisor 17
The end of pipe 17 connects four longitudinally disposed and equally distributed hydrogen conveying arms 18, and the lower section of hydrogen conveying arm 18 sets
Be equipped with a horizontal circle Hydrogen distribution device 19, the end of four hydrogen conveying arms 18 respectively with circular Hydrogen distribution device 19
Connecting, circular Hydrogen distribution device 19 is positioned at the lower section of tubing heat exchanger 16, Hydrogen distribution device 19 include being coaxially disposed interior in
Outer 3 ring shape Hydrogen distribution pipes 20, each annular Hydrogen distribution pipe 20 is provided with several hydrogen dispersion hole 21.
Use the method, from the parameter of materials of extraction at the bottom of dehydrogenation tower 9 tower be finally:
Temperature: 100 DEG C；
Pressure: 0.12MPaG
Composition: Ketohexamethylene: 90wt%, water: 0.2wt%, Hexalin: 7.5wt%, phenol: 1.5wt%, light component: 0.4wt%, restructuring
Point: 0.4wt%.
Specific embodiment two
With above-described embodiment one, its difference is:
In step (1), raw material phenol is heated to 120 DEG C through phenol preheater 1；Controlling phenol carburator 2 top pressure is
0.20MPaG；The admixture of gas being made up of phenol and decarburization hydrogen in raw material superheater 3 is superheated to 175 DEG C；Phenol with
The mol ratio of hydrogen is 1:2, and hydrogen is 5:1 with the mol ratio of nitrogen；Wherein in the preparation process of decarburization hydrogen: oxidation of coal is closed
Thing content be the raw hydrogen of 20ppm after hydrogen preheater 4 is preheated to 160 DEG C, then be heated to temperature through hydrogen heater 5 and be
Decarburizing reaction device 8 is sent into after 230 DEG C；It is 235 DEG C that decarburizing reaction temperature controls, and Stress control is 1.1MPaG.
In step (2), it is 195 DEG C that the reaction mass temperature in hydrogenation reactor 6 controls, and Stress control is 0.1MPaG.
In step (3), in hydrogenation reactor heat recovering heat exchanger 7, hydrogenation reaction product and decarburization hydrogen carry out heat friendship
Changing, hydrogenation reaction product temperature is down to 105 DEG C.
In step (4), controlling to be 0.05MPaG by the tower top pressure of dehydrogenation tower 9, obtaining temperature at the bottom of the tower of dehydrogenation tower 9 is 95
DEG C Ketohexamethylene crude product.Wherein gas is sent into and is reclaimed hydrogen gas compressor 13 by boost in pressure to 0.2MPaG；Control discharge system
Gas flow be 0.005 mol% reclaiming hydrogen total amount, to enter hydrogenation anti-to maintain to give off the gas flow of system by control
The content answering the gaseous impurity (methane etc.) of device 6 is 4 mol%.
Use this process, from the parameter of materials of extraction at the bottom of dehydrogenation tower 9 tower be finally:
Temperature: 95 DEG C；
Pressure: 0.05MPaG
Composition: Ketohexamethylene: 90wt%, water: 0.2wt%, Hexalin: 7.6wt%, phenol: 1.4wt%, light component: 0.35wt%, restructuring
Point: 0.45wt%.
Specific embodiment three
With above-described embodiment one, its difference is:
In step (1), raw material phenol is heated to 140 DEG C through phenol preheater 1；Controlling phenol carburator 2 top pressure is
0.25MPaG；The admixture of gas being made up of phenol and decarburization hydrogen in raw material superheater 3 is superheated to 195 DEG C；Phenol with
The mol ratio of hydrogen is 1:6, and hydrogen is 2:1 with the mol ratio of nitrogen；Wherein in the preparation process of decarburization hydrogen: by carbon content be
The raw hydrogen of 30ppm is after hydrogen preheater 4 is preheated to 170 DEG C, then is heated to after temperature is 240 DEG C through hydrogen heater 5
Send into decarburizing reaction device 8；It is 245 DEG C that decarburizing reaction temperature controls, and Stress control is 1.3MPaG.
In step (2), controlling to be 180 DEG C by the reaction mass temperature in hydrogenation reactor 6, Stress control is 0.2MPaG.
In step (3), in hydrogenation reactor heat recovering heat exchanger 7, hydrogenation reaction product and decarburization hydrogen carry out heat friendship
Changing, hydrogenation reaction product temperature is down to 115 DEG C.
In step (4), controlling to be 0.15MPaG by the tower top pressure of dehydrogenation tower 9, obtaining temperature at the bottom of the tower of dehydrogenation tower 9 is
The Ketohexamethylene crude product of 105 DEG C.Gas is sent into and is reclaimed hydrogen gas compressor 13 by boost in pressure to 0.3MPaG；Control discharge system
Gas flow be 0.01 mol% reclaiming hydrogen total amount, to enter hydrogenation anti-to maintain to give off the gas flow of system by control
The content answering the gaseous impurity (methane etc.) of device 6 is 1 mol%.
Use the method, from the parameter of materials of extraction at the bottom of dehydrogenation tower 9 tower be finally:
Temperature: 105 DEG C；
Pressure: 0.15MPaG
Composition: Ketohexamethylene: 90.1wt%, water: 0.2wt%, Hexalin: 7.5wt%, phenol: 1.4wt%, light component: 0.38wt%, weight
Component: 0.42wt%.
Specific embodiment four
The system of a kind of phenol production Ketohexamethylene method for above-mentioned specific embodiment one, as it is shown in figure 1, include that phenol preheats
Device 1, phenol carburator 2, raw material superheater 3, hydrogen preheater 4, hydrogen heater 5, hydrogenation reactor 6, hydrogenation reactor heat
Reclaiming heat exchanger 7, decarburizing reaction device 8 and dehydrogenation tower 9, phenol preheater 1 is connected with the sidepiece charging aperture of phenol carburator 2, benzene
The top discharge mouth of phenol carburator 2 is connected with the import of raw material superheater 3, the outlet of raw material superheater 3 and hydrogenation reactor 6
Its top feed mouth connects, and the bottom discharge mouth of hydrogenation reactor 6 is connected with the import of hydrogenation reactor heat recovering heat exchanger 7, adds
The outlet of hydrogen reactor heat recovering heat exchanger 7 is connected with the lower end charging aperture of dehydrogenation tower 9, and one end of hydrogen preheater 4, hydrogen add
Hot device 5, decarburizing reaction device 8 are in turn connected to form closed circuit with the other end of hydrogen preheater 4, and hydrogen preheater 4 is by adding
Hydrogen reactor heat recovering heat exchanger 7 is connected with the lower end air inlet of phenol carburator 2, and the bottom of dehydrogenation tower 9 is provided with Ketohexamethylene
Product outlet 10.
In this particular embodiment, the top gas phase exit of dehydrogenation tower 9 is provided with the first overhead condenser 11, the first tower
The liquid-phase outlet of top condenser 11 is connected with the upper end refluxing opening of dehydrogenation tower 9 by overhead reflux pump 12, the first overhead condenser
The gaseous phase outlet of 11 connects recovery hydrogen gas compressor 13, reclaims hydrogen gas compressor 13 and connects the second overhead condenser 14, and second
The liquid-phase outlet of overhead condenser 14 is connected with the upper end import of dehydrogenation tower 9 by overhead reflux pump 12, the second overhead condenser
The gaseous phase outlet of 14 is connected with hydrogenation reactor heat recovering heat exchanger 7.The number of plates of dehydrogenation tower 9 is 7 layers of valve plate.
In this particular embodiment, as shown in Figures 2 and 3, the cylinder of phenol carburator 2 is interior and is positioned at phenol carburator 2
The lower horizontal of sidepiece charging aperture 15 be provided with dismountable tubing heat exchanger 16, the barrel upper water of phenol carburator 2
The flat hydrogen inlet that is provided with is responsible for 17, extends the center in phenol carburator 2 cylinder, hydrogen inlet master in hydrogen inlet supervisor 17
The end of pipe 17 connects four longitudinally disposed and equally distributed hydrogen conveying arms 18, and the lower section of hydrogen conveying arm 18 sets
Be equipped with a horizontal circle Hydrogen distribution device 19, the end of four hydrogen conveying arms 18 respectively with circular Hydrogen distribution device 19
Connecting, circular Hydrogen distribution device 19 is positioned at the lower section of tubing heat exchanger 16, Hydrogen distribution device 19 include being coaxially disposed interior in
Outer 3 ring shape Hydrogen distribution pipes 20, each annular Hydrogen distribution pipe 20 is provided with several hydrogen dispersion hole 21.
Certainly, described above not limitation of the present invention, the present invention is also not limited to the example above.The art
Change that those of ordinary skill is made in the essential scope of the present invention, retrofit, add or replace, also should belong to present invention protection
Scope.
Claims (10)
1. the method for a phenol production Ketohexamethylene, it is characterised in that comprise the following steps:
Raw material phenol is sent into after phenol preheater is heated to 120-140 DEG C phenol carburator, in phenol carburator, controls
Phenol carburator top pressure is 0.2-0.25MPaG, and phenol is heated dual function, phenol vapour by decarburization hydrogen partial pressure and steam
Formation gas and decarburization hydrogen are mixed and send into raw material superheater, are made up of phenol and decarburization hydrogen in raw material superheater
Hydrogenation reactor sent into by admixture of gas after being superheated to 175-195 DEG C of activation, and the gas controlling to enter hydrogenation reactor mixes
In compound, phenol is 1:2-1:6 with the mol ratio of hydrogen；
(2) controlling the reaction temperature of hydrogenation reactor for 180-195 DEG C, Stress control is 0.1-0.2MPaG, anti-at hydrogenation
In answering device, phenol hydrogenation generates Ketohexamethylene, and with generating by-product cyclic hexanol, wherein hydrogenation reactor is calandria type fixed bed
Isothermal reactor, calandria type fixed bed isothermal reactor is built with Al2O3Pd catalyst for carrier；
(3) hydrogenation reaction product is sent into hydrogenation reactor heat recovering heat exchanger bottom hydrogenation reactor, in hydrogenation reaction
In device heat recovering heat exchanger, hydrogenation reaction product and decarburization hydrogen carry out heat exchange, and the decarburization hydrogen after intensification sends into phenol vaporization
Device, the hydrogenation reaction product being cooled to 105-115 DEG C sends into dehydrogenation tower；
(4) control to be 0.05-0.15MPaG by the tower top pressure of dehydrogenation tower, hydrogenation reaction product is separated, dehydrogenation tower
Tower top obtains unreacted hydrogen, obtains the Ketohexamethylene crude product that temperature is 95-105 DEG C at the bottom of the tower of dehydrogenation tower.
The method of phenol production Ketohexamethylene the most according to claim 1, it is characterised in that the decarburization hydrogen described in step (1)
The preparation technology flow process of gas is: through hydrogen preheater, the raw hydrogen that hydrocarbon content is 20-30ppm is preheated to 160-
After 170 DEG C, then it is heated to after temperature is 230-240 DEG C sending into insulation fix bed formula decarburizing reaction device through hydrogen heater；De-
Removing the carbon monoxide in raw hydrogen and carbon dioxide in carbon reactor, decarburizing reaction uses Al2O3Ni for carrier is catalyzed
Agent, decarburizing reaction temperature controls as 235-245 DEG C, and Stress control is 1.1-1.3MPaG, obtain after carbonization treatment carbon monoxide and
The concentration of total carbon dioxide decarburization hydrogen less than 2ppb, sends decarburization hydrogen into hydrogen preheater, raw material in hydrogen preheater
Hydrogen and decarburization hydrogen carry out heat exchange, and the decarburization hydrogen hydrogenated reactor heat recovering heat exchanger after cooling sends into benzene after heating up
Phenol carburator.
The method of phenol production Ketohexamethylene the most according to claim 1, it is characterised in that: the tower of dehydrogenation tower in step (4)
Top gas after the first overhead condenser is cooled to 40 DEG C liquid after gas-liquid separation, separation through overhead reflux pumped back dehydrogenation
Top of tower as backflow, gas send into reclaim hydrogen gas compressor by after boost in pressure to 0.2-0.3MPaG through the second overhead condensation
Device cooling the liquid after gas-liquid separation, separation send dehydrogenation top of tower back to, and the gas hydrogenated reactor recuperation of heat of major part is changed
Sending into phenol carburator after hot device heat temperature raising, residue small part discharges system.
The method of phenol production Ketohexamethylene the most according to claim 3, it is characterised in that: control the gas flow of discharge system
For reclaiming the 0.005-0.01 mol% of hydrogen total amount.
The method of phenol production Ketohexamethylene the most according to claim 1, it is characterised in that the entrance described in step (1) adds
In the admixture of gas of hydrogen reactor, hydrogen controls as 5:1-2:1 with the mol ratio of nitrogen.
The method of phenol production Ketohexamethylene the most according to claim 1, it is characterised in that: described hydrogenation reactor is divided into
Upper reaction section and bottom cooling section, described hydrogenation reactor is sent into hydrogenation reactor shell-side with boiler feedwater and is produced 0.2-
The saturated vapor of 0.3MPaG.
7. the system for the method for the phenol production Ketohexamethylene described in claim 1, it is characterised in that: include that phenol is pre-
Hot device, phenol carburator, raw material superheater, hydrogen preheater, hydrogen heater, hydrogenation reactor, hydrogenation reactor recuperation of heat
Heat exchanger, decarburizing reaction device and dehydrogenation tower, described phenol preheater is connected with the sidepiece charging aperture of described phenol carburator,
The top discharge mouth of described phenol carburator is connected with the import of described raw material superheater, going out of described raw material superheater
Mouth is connected with its top feed mouth of described hydrogenation reactor, the bottom discharge mouth of described hydrogenation reactor and described hydrogenation
The import of reactor heat recovering heat exchanger connects, the outlet of described hydrogenation reactor heat recovering heat exchanger and described dehydrogenation tower
Lower end charging aperture connect, one end of described hydrogen preheater, described hydrogen heater, described decarburizing reaction device and institute
The other end of the hydrogen preheater stated is in turn connected to form closed circuit, and described hydrogen preheater is by described hydrogenation reaction
Device recuperation of heat reactor is connected with the lower end air inlet of described phenol carburator, and the bottom of described dehydrogenation tower is provided with hexamethylene
Ketone product outlet.
The system of phenol production Ketohexamethylene the most according to claim 7, it is characterised in that: the top gas of described dehydrogenation tower
Phase exit is provided with the first overhead condenser, and the liquid-phase outlet of the first described overhead condenser passes through overhead reflux pump and institute
The upper end import of the dehydrogenation tower stated connects, and the gaseous phase outlet of the first described overhead condenser connects recovery hydrogen gas compressor,
Described recovery hydrogen gas compressor connects the second overhead condenser, and the liquid-phase outlet of the second described overhead condenser passes through tower top
Reflux pump is connected with the upper end import of described dehydrogenation tower, the gaseous phase outlet of the second described overhead condenser and described hydrogenation
Reactor heat recovering heat exchanger connects.
The system of phenol production Ketohexamethylene the most according to claim 7, it is characterised in that: described dehydrogenation tower is board-like steaming
Evaporating tower, column plate can be float valve or sieve plate, and the number of plates is 5-10 layer.
The system of phenol production Ketohexamethylene the most according to claim 7, it is characterised in that: described phenol carburator
In cylinder and the lower horizontal of the sidepiece charging aperture that is positioned at described phenol carburator is provided with dismountable tubing heat exchanger,
The barrel upper level of described phenol carburator is provided with hydrogen inlet supervisor, extends cylinder in described hydrogen inlet supervisor
Interior center, the end of described hydrogen inlet supervisor connects four longitudinally disposed and equally distributed hydrogen conveying arms,
The lower section of described hydrogen conveying arm is provided with a horizontal circle Hydrogen distribution device, four described hydrogen conveying arms
End be connected with described circular Hydrogen distribution device respectively, described circular Hydrogen distribution device is positioned at described tubular heat exchange
The lower section of device, described circular Hydrogen distribution device includes the interior China and foreign countries 3 ring shape Hydrogen distribution pipe being coaxially disposed, and each is described
It is provided with several hydrogen dispersion hole on annular Hydrogen distribution pipe.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3305586A (en) * | 1959-05-15 | 1967-02-21 | Stamicarbon | Process for preparing cyclohexanone |
| US4162267A (en) * | 1978-06-22 | 1979-07-24 | Allied Chemical Corporation | Production of cyclohexanone |
| CN101945845A (en) * | 2007-12-20 | 2011-01-12 | 帝斯曼知识产权资产管理有限公司 | Cyclohexanone production process with modified post-distillation |
| CN102391085A (en) * | 2011-08-11 | 2012-03-28 | 河北美邦工程科技有限公司 | Process for producing cyclohexanone by performing incomplete hydrogenation |
| CN102875348A (en) * | 2012-09-29 | 2013-01-16 | 中国天辰工程有限公司 | High-yield production method of cyclohexanone |
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2016
- 2016-06-02 CN CN201610388594.7A patent/CN105967984B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3305586A (en) * | 1959-05-15 | 1967-02-21 | Stamicarbon | Process for preparing cyclohexanone |
| US4162267A (en) * | 1978-06-22 | 1979-07-24 | Allied Chemical Corporation | Production of cyclohexanone |
| CN101945845A (en) * | 2007-12-20 | 2011-01-12 | 帝斯曼知识产权资产管理有限公司 | Cyclohexanone production process with modified post-distillation |
| CN102391085A (en) * | 2011-08-11 | 2012-03-28 | 河北美邦工程科技有限公司 | Process for producing cyclohexanone by performing incomplete hydrogenation |
| CN102875348A (en) * | 2012-09-29 | 2013-01-16 | 中国天辰工程有限公司 | High-yield production method of cyclohexanone |
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