CN105967984B - The method and system of phenol production cyclohexanone - Google Patents
The method and system of phenol production cyclohexanone Download PDFInfo
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- CN105967984B CN105967984B CN201610388594.7A CN201610388594A CN105967984B CN 105967984 B CN105967984 B CN 105967984B CN 201610388594 A CN201610388594 A CN 201610388594A CN 105967984 B CN105967984 B CN 105967984B
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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
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
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- 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
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention discloses the method and system of phenol production cyclohexanone, feature is to comprise the following steps：Raw material phenol is sent into phenol vaporizer after the heating of phenol preheater, the mixed gas of phenol and decarburization hydrogen is sent into raw material superheater, hydrogenation reactor is sent into after overheat, phenol hydrogenation generates cyclohexanone in hydrogenation reactor, hydrogenation reaction product is sent into hydrogenation reactor heat recovering heat exchanger and is sent into dehydrogenation tower after recycling heat, separate unreacted hydrogen, the bottom of towe of dehydrogenation tower obtains cyclohexanone crude product, its system includes phenol preheater, phenol vaporizer, raw material superheater, hydrogen preheater, hydrogen heater, hydrogenation reactor, hydrogenation reactor heat recovering heat exchanger, decarburizing reaction device and dehydrogenation tower, advantage is to realize phenol high efficiency, Hydrogenation is for cyclohexanone with high selectivity, technological process is simple, product cyclohexanone high income.
Description
Technical field
The present invention relates to a kind of cyclohexanone production process, a kind of method more particularly, to phenol production cyclohexanone and it is
System.
Background technology
Cyclohexanone is a kind of very extensive industrial chemicals of application, is played an important role in industrial production, daily life.
By its purposes, cyclohexanone be divided into acid amides use and two major classes of non-acid amides, wherein 70% is acid amides cyclohexanone.Common 6 He of nylon
Nylon66 fiber is exactly to be prepared with cyclohexanone.Further, since cyclohexanone has the characteristics that highly dissoluble and low volatility, can make
Used for organic solvent, i.e., non-acid amides cyclohexanone.For nitrocotton, cellulose, nitrocellulose, polyurethane, chloroethylene polymerization
The polymer such as thing and copolymer is a kind of preferable solvent；Cyclohexanone is used in mixed way with other solvents, adjustable systems evaporation speed
Degree；In leather industry, cyclohexanone can do degreasing agent and detergent, for cleaning reactor；In addition, cyclohexanone is led in medicine
Domain, antiaging agent etc. are also widely used；For example, it is by cyclohexanone and cyanogen that special Maron, cough U.S.A, which such as cut at the pharmaceutical intermediate,
Acetic acidreaction, is made after processing.
At present, the industrial process of cyclohexanone 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 characteristics of cyclohexane oxidation process is：For
Improve the security 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 feedstocks need a large amount of cycling and reutilizations, this just needs to consume substantial amounts of energy, from
And make it that this process energy consumption is very high, and it is high with the presence of explosive mixture, System risk in reaction process.
Cyclohexene hydration method is a kind of more advanced cyclohexanone production process of appearance after cyclohexane oxidation process.Cyclohexene
The characteristics of hydration method is：When producing intermediate product cyclohexene, since hexamethylene is more more stable than cyclohexene, hexamethylene hydrogenation life
, can the substantial amounts of hexamethylene of by-product during producing cyclohexene.And final products cyclohexanone is produced, also need by cyclohexene water
Cyclohexanol is produced in symphysis, and cyclohexanol dehydrogenation process, technological process length, high energy consumption, equipment is more, and investment is big.And given birth to using this technique
The cyclohexanone of production is since flow is very long, and impurity composition is more in the cyclohexanone that final production goes out, so as to cause cyclohexene hydration method
When the cyclohexanone of production is used to produce caprolactam, the caprolactam impurity content produced is more, and it is high to be usually not used to production
Hold spinning.
Phenol hydrogenation method is to produce another important method of cyclohexanone, its technological principle and cyclohexane oxidation process and hexamethylene
Alkene hydration method is different, since, there are oxygen, it can obtain cyclohexanone by one step of hydrogenation reaction on its phenyl ring.Production
Technique is simple, and flow is very short, and the cyclohexanone quality of this technique productions is good, and impurity content is low, is widely used in the high-end downstream of production
Product.But phenol hydrogenation reaction hydrogenation is difficult, how the difficult control of side reaction, improve hydrogenation efficiency, improve target product cyclohexanone
Yield be phenol hydrogenation production cyclohexanone technology problem.
Phenol hydrogenation production cyclohexanone fundamental reaction principle is as follows：
How first step reaction activation is effectively realized, can it be that realize the key of the technology that second step hydrogenation reaction occur.
Moreover, during the preparing cyclohexanone from phenol, cyclohexanol accessory substance is often produced.Therefore how effectively to reduce accessory substance,
Realize high efficiency, the phenol hydrogenation of high selectivity prepares the key that cyclohexanone is technology.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of flow is simple, raw material availability is high, target product hexamethylene
The method and system of the few phenol production cyclohexanone of ketone high income, cyclohexanone impurity content.
Technical solution is used by the present invention solves above-mentioned technical problem：A kind of method of phenol production cyclohexanone, bag
Include following steps：
（1）Raw material phenol is sent into phenol vaporizer after phenol preheater is heated to 120-140 DEG C, in phenol vaporizer
In, it is 0.2-0.25MPaG to control phenol vaporizer top pressure, and phenol is heated double action by decarburization hydrogen partial pressure and steam,
Phenol is vaporized into gas and decarburization hydrogen is mixed and is sent into raw material superheater, by phenol and decarburization hydrogen in raw material superheater
The admixture of gas of composition is sent into hydrogenation reactor after being superheated to 175-195 DEG C of activation, and controls into hydrogenation reactor
The molar ratio of phenol and hydrogen is 1 in admixture of gas:2-1:6；
（2）It it is 180-195 DEG C by the reaction temperature control of hydrogenation reactor, pressure control is 0.1-0.2MPaG, is being added
Phenol hydrogenation generates cyclohexanone in hydrogen reactor, and with generation by-product cyclic hexanol；Wherein hydrogenation reactor is consolidated for shell and tube
Fixed bed isothermal reactor, calandria type fixed bed isothermal reactor is interior to be equipped with Al2O3For the Pd catalyst of carrier；
（3）Hydrogenation reaction product is sent into hydrogenation reactor heat recovering heat exchanger from hydrogenation reactor bottom, is being hydrogenated with
Hydrogenation reaction product carries out heat exchange with decarburization hydrogen in reactor heat recovering heat exchanger, and the decarburization hydrogen after heating is sent into phenol
Vaporizer, is cooled to 105-115 DEG C of hydrogenation reaction product and is sent into dehydrogenation tower；
（4）It is 0.05-0.15MPaG by the tower top pressure control of dehydrogenation tower, hydrogenation reaction product is separated, dehydrogenation
The tower top of tower obtains unreacted hydrogen, and the bottom of towe of dehydrogenation tower obtains the cyclohexanone crude product that temperature is 95-105 DEG C.
Step（1）Described in the preparation process flow of decarburization hydrogen be：It is 20-30ppm's by hydrocarbon content
Raw hydrogen is after hydrogen preheater is preheated to 160-170 DEG C, then thermal insulation is sent into after hydrogen heater is heated to 230-240 DEG C
Fixed-bed type decarburizing reaction device；The carbon monoxide and carbon dioxide in raw hydrogen, decarburizing reaction are removed in decarburizing reaction device
Using Al2O3For the Ni catalyst of carrier, decarburizing reaction temperature control is 235-245 DEG C, and pressure control is 1.1-1.3MPaG, is taken off
Carbon monoxide is obtained after carbon processing and concentration of total carbon dioxide is less than the decarburization hydrogen of 2ppb, decarburization hydrogen is sent into hydrogen preheating
Device, raw hydrogen carries out heat exchange with decarburization hydrogen in hydrogen preheater, the hydrogenated reactor heat of the decarburization hydrogen after cooling
Phenol vaporizer is sent into after recycling heat exchanger heating.Removal of carbon monoxide, carbon dioxide can be to avoid Pyrogentisinic Acid's hydrogenation catalysts
Poison.
Step（4）The top gaseous phase of middle dehydrogenation tower is after the first overhead condenser is cooled to 40 DEG C through gas-liquid separation, separation
Liquid afterwards through overhead reflux pumped back dehydrogenation top of tower as flowing back, be sent into recycling hydrogen gas compressor and arrive boost in pressure by gas
Cooled down and through gas-liquid separation through the second overhead condenser after 0.2-0.3MPaG, the liquid after separation sends dehydrogenation top of tower, gas back to
Phenol vaporizer, remaining small part discharge system are sent into after most of hydrogenated reactor heat recovering heat exchanger heat temperature raising.
The gas flow control of above-mentioned discharge system is the 0.005-0.01 mol% of recycling hydrogen total amount, is discharged by controlling
Go out the gas flow of system to maintain the gaseous impurity into hydrogenation reactor（Methane etc.）Content be 1 mol% -4 mol%, from
And maintain effective progress of hydrogenation reaction.Test and find through inventor：After methane content is more than 4mol% in hydrogen, hydrogenation is anti-
The selectivity answered significantly reduces, and if to maintain methane content in hydrogen to be consistently lower than 1mol%, need discharge a large amount of in system
Gas could maintain.Through experimental test, the gaseous impurity into hydrogenation reactor is maintained（Methane）Content be 1mol%-
4mol% is optimal.
Step（1）The control of the molar ratio of hydrogen and nitrogen is 5 in the admixture of gas into hydrogenation reactor:1-
2:1.Rational nitrogen content, reduces reactor coking and improves target product selectivity.
The hydrogenation reactor is divided into upper reaction section and lower part cooling section, and the hydrogenation reactor is with boiler feedwater
It is sent into the saturated vapor that hydrogenation reactor shell-side produces 0.2-0.3MPaG.It it is 190 DEG C for controlling temperature in hydrogenation reactor 6.
Lower part cooling section is mainly quick to reduce upper reaction section hydrogenation products temperature, effectively suppresses the generation of side reaction, and carry at the same time
High heat organic efficiency.
A kind of system for above-mentioned phenol production cyclohexanone method, including phenol preheater, phenol vaporizer, raw material mistake
Hot device, hydrogen preheater, hydrogen heater, hydrogenation reactor, hydrogenation reactor heat recovering heat exchanger, decarburizing reaction device and dehydrogenation
Tower, the phenol preheater are connected with the sidepiece feed inlet of the phenol vaporizer, the top of the phenol vaporizer
Discharge port is connected with the import of the raw material superheater, outlet and the hydrogenation reactor of the raw material superheater
Its top feed mouth connects, the bottom discharge mouth of the hydrogenation reactor and the hydrogenation reactor heat recovering heat exchanger into
Mouth connection, the outlet of the hydrogenation reactor heat recovering heat exchanger is connected with the lower end feed inlet of the dehydrogenation tower, described
One end of hydrogen preheater, the hydrogen heater, the decarburizing reaction device it is another with the hydrogen preheater
End is in turn connected to form circulation loop, the hydrogen preheater by the hydrogenation reactor recuperation of heat reactor with it is described
Phenol vaporizer the connection of lower end air inlet, the bottom of the dehydrogenation tower is provided with cyclohexanone product outlet.
The top gas phase exit of the dehydrogenation tower is provided with the first overhead condenser, first overhead condenser
Liquid-phase outlet pumped by overhead reflux and be connected with the upper end import of the dehydrogenation tower, the gas of first overhead condenser
Mutually outlet connection recycling hydrogen gas compressor, the recycling hydrogen gas compressor connect the second overhead condenser, second tower
The liquid-phase outlet for pushing up condenser is connected by overhead reflux pump with the upper end import of the dehydrogenation tower, and second tower top is cold
The gaseous phase outlet of condenser is connected with the hydrogenation reactor heat recovering heat exchanger.
The dehydrogenation tower is plate tower, and column plate can be float valve or sieve plate, and the number of plates is 5-10 layers.Using dehydrogenation tower
Hydrogen is separated to recycle from hydrogenation products, bottom of towe cyclohexanone crude product temperature is 95-105 DEG C after separation.Conventional skill
Art is that the gas-liquid mixture that hydrogenation reactor heat recovering heat exchanger is discharged is cooled to 50 DEG C by whole materials by refrigerant, then
Gas-liquid separation is carried out, obtains hydrogen and cyclohexanone crude product that temperature is 50 DEG C.And the cyclohexanone crude product that the present invention obtains
Temperature is 95-105 DEG C, can significantly reduce subsequent fine and evaporate separated energy consumption, while saves cold, and energy-saving effect is notable.
The lower horizontal of sidepiece feed inlet in the cylinder of the phenol vaporizer and positioned at the phenol vaporizer
Dismountable tubing heat exchanger is provided with, the barrel upper level of the phenol vaporizer is provided with hydrogen inlet supervisor,
The center in cylinder is extended in the hydrogen inlet supervisor, the end of hydrogen inlet supervisor is connected with four longitudinal directions and sets
Put and equally distributed hydrogen delivery branch pipe, a horizontal circle hydrogen point is provided with below the hydrogen delivery branch pipe
Cloth device, the end of the hydrogen delivery branch pipe described in four are connected with the circular Hydrogen distribution device respectively, the circular hydrogen
Gas distributor is located at the lower section of the tubing heat exchanger, and the circular Hydrogen distribution device includes being coaxially disposed inside and outside
3 ring shape Hydrogen distribution pipes, are both provided with several hydrogen dispersion holes on each annular Hydrogen distribution pipe.This structure
Hydrogen and raw material phenol are more fully mixed, and can effectively reduce the vapourizing temperature of phenol.
Compared with prior art, the advantage of the invention is that：
（1）It is 1 to control into the phenol of raw material superheater and the molar ratio of decarburization hydrogen:2-1:6, go out raw material superheater
Temperature of charge is 175-195 DEG C, effectively realizes the efficient activation of phenol.
（2）It is 5 to control into the decarburization hydrogen of hydrogenation reactor and the molar ratio of nitrogen:1-2:1.The reasonable concentration of nitrogen
The selectivity of reaction can be improved, increases the service life of catalyst.
（3）Decarburization hydrogen is passed through in phenol vaporizer liquid, benzene in phenol vaporizer is reduced using decarburization hydrogen partial pressure
The vapourizing temperature of phenol, makes phenol vapourizing temperature in phenol vaporizer be reduced to 150-160 DEG C by 180 DEG C.
（4）It is 175-195 DEG C to control raw material superheater outlet temperature, so as to ensure that the conversion ratio of hydrogenation reaction and yield are equal
It is very high.
（5）Hydrogenation reactor is calandria type fixed bed reactor, and reactor is divided into upper reaction section and lower part cooling section.Under
Portion's cooling section can quickly reduce hydrogenation products temperature, effectively reduce the generation of side reaction.Fully recycling reacts what is released at the same time
Heat, can finally control hydrogenation reaction product go out hydrogenation reactor temperature be 150 DEG C.
（6）Hydrogen is separated from hydrogenation products using destilling tower, cyclohexanone crude product temperature is 95-105 DEG C after separation（Often
Rule use the isolated hydrogenation products temperature that cools down as 40-50 DEG C）, subsequent fine can be significantly reduced and evaporate separated energy consumption, together
When save cold, energy-saving effect is notable.
（7）By setting hydrogen decarburizing reaction device, ensure to be sent into carbon monoxide, the total carbon dioxide content of hydrogenation reactor
Less than 2ppb, so as to avoid carbon monoxide, carbon dioxide from poisoning hydrogenation catalyst, catalyst service life is improved.
（8）Reaction method and system under the present invention finally can be achieved phenol conversion and be more than 99 wt %, cyclohexanone selection
Rate is more than 90 wt %, and cyclohexanone+cyclohexanol selection rate is more than 99 wt %.
Brief description of the drawings
Fig. 1 is the process flow chart of the method and system of phenol production cyclohexanone of the present invention；
Fig. 2 is the structure diagram one of phenol vaporizer of the present invention；
Fig. 3 is the structure diagram two of phenol vaporizer of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with attached drawing embodiment.
Specific embodiment one
A kind of method of phenol production cyclohexanone, as shown in Figure 1, comprising the following steps：
（1）Raw material phenol is sent into phenol vaporizer 2 after phenol preheater 1 is heated to 130 DEG C, in phenol vaporizer 2
In, it is 0.22MPaG to control 2 top pressure of phenol vaporizer, and phenol is heated double action, benzene by decarburization hydrogen partial pressure and steam
Phenol is vaporized into gas and decarburization hydrogen is mixed and is sent into raw material superheater 3, by phenol and decarburization hydrogen in raw material superheater 3
The admixture of gas of composition is sent into hydrogenation reactor 6, gas mixing of the control into hydrogenation reactor 6 after being superheated to 185 DEG C
The molar ratio of phenol and hydrogen is 1 in thing:5；Mole of hydrogen and nitrogen in controlling into the admixture of gas of hydrogenation reactor 6
Than for 3:1；
（2）The reaction mass temperature for controlling hydrogenation reactor 6 is 190 DEG C, pressure 0.15MPaG, in hydrogenation reactor 6
Interior phenol hydrogenation generates cyclohexanone, and hydrogenation reactor 6 is calandria type fixed bed reactor, is equipped with calandria type fixed bed reactor
Al2O3For the Pd catalyst of carrier；
（3）Hydrogenation reaction product is sent into hydrogenation reactor heat recovering heat exchanger 7 from 6 bottom of hydrogenation reactor, is being added
Hydrogenation reaction product carries out heat exchange, the temperature of decarburization hydrogen after heat exchange with decarburization hydrogen in hydrogen reactor heat recovering heat exchanger 7
For 125 DEG C, phenol vaporizer 2 is then fed into；Hydrogenation reaction product temperature after cooling is 112 DEG C, is sent into dehydrogenation tower 9；
（4）It is 0.12MPaG by the tower top pressure control of dehydrogenation tower 9, hydrogenation reaction product is separated, dehydrogenation tower 9
Tower top obtains unreacted hydrogen, and the bottom of towe of dehydrogenation tower 9 obtains the cyclohexanone crude product that temperature is 100 DEG C.Wherein dehydrogenation tower 9 is
Destilling tower, the hydrogen in hydrogenation reaction product is separated using destilling tower, and cyclohexanone crude product temperature is 100 DEG C after separation.Hexamethylene
Ketone crude product temperature is high, can reduce subsequent fine and evaporate separated energy consumption, while saves cold, and energy-saving effect is notable.
In this particular embodiment, the preparation flow of decarburization hydrogen is：By the feed hydrogen that hydrocarbon content is 25ppm
Gas brings up to 235 DEG C after hydrogen preheater 4 is preheated to 165 DEG C, through 5 temperature of hydrogen heater, 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, 240 DEG C of reaction temperature,
Pressure control is 1.2MPaG, and carbon monoxide is obtained after carbonization treatment and concentration of total carbon dioxide is less than the decarburization hydrogen of 2ppb, will
Decarburization hydrogen is sent into hydrogen preheater 4, and raw hydrogen carries out heat exchange with decarburization hydrogen in hydrogen preheater 4, warm after cooling
Spend and be sent into hydrogenation reaction together with recycling hydrogen and the nitrogen of supplement from the second overhead condenser 14 for 115 DEG C of decarburization hydrogen
Device heat recovering heat exchanger 7, is sent into phenol vaporizer 2 after heating.
Above-mentioned steps（4）The top gaseous phase of middle dehydrogenation tower 9 is after the first overhead condenser 11 is cooled to 40 DEG C through gas-liquid point
From the liquid after separation is sent to 9 overhead reflux of dehydrogenation tower through overhead reflux pump 12, and gas is sent into recycling hydrogen gas compressor 13 and will be pressed
To being cooled to 40 DEG C and through gas-liquid separation through the second overhead condenser 14 after 0.25MPaG, the liquid after separation is sent back to de- for power lifting
The top of hydrogen tower 9, largely the hydrogenated heating of reactor heat recovering heat exchanger 7 rises the gas of the top of the second overhead condenser 14 outflow
Phenol vaporizer 2, remaining partial gas discharge system are sent into after warm to 125 DEG C.The gas flow for controlling discharge system is recycling
0.008 mol% of hydrogen total amount.Control the gas for entering hydrogenation reactor 6 miscellaneous by controlling the gas flow for the system that gives off
The content of matter methane is 3mol%, so as to ensure the efficient progress of hydrogenation reaction.Hydrogenation reactor 6 divide be upper reaction section and under
Portion's cooling section, the saturated vapor that hydrogenation reactor 6 is sent into 6 shell-side of hydrogenation reactor generation 0.2-0.3MPaG with boiler feedwater are used
It it is 190 DEG C in controlling temperature in hydrogenation reactor 6.
In this particular embodiment, as shown in Figures 2 and 3, the cylinder of phenol vaporizer 2 is interior and is located at phenol vaporizer 2
The lower horizontal of sidepiece feed inlet 15 be provided with dismountable tubing heat exchanger 16, the barrel upper water of phenol vaporizer 2
It is flat to be provided with hydrogen inlet supervisor 17, the center in 2 cylinder of phenol vaporizer, hydrogen inlet master are extended in hydrogen inlet supervisor 17
The end of pipe 17 is connected with four longitudinally disposed and equally distributed hydrogen delivery branch pipes 18, and the lower section of hydrogen delivery branch pipe 18 is set
Be equipped with a horizontal circle Hydrogen distribution device 19, the ends of four hydrogen delivery branch pipes 18 respectively with circular Hydrogen distribution device 19
Connection, circular Hydrogen distribution device 19 be located at the lower section of tubing heat exchanger 16, Hydrogen distribution device 19 including be coaxially disposed it is interior in
Outer 3 ring shape Hydrogen distribution pipe 20, is both provided with several hydrogen dispersion holes 21 on each annular Hydrogen distribution pipe 20.
Using the method, it is from the parameter of materials of 9 bottom of towe of dehydrogenation tower extraction finally：
Temperature：100℃；
Pressure：0.12MPaG
Composition：Cyclohexanone：90wt%, water：0.2wt%, cyclohexanol：7.5wt%, phenol：1.5wt%, light component：0.4wt%,
Heavy constituent：0.4wt%.
Specific embodiment two
With above-described embodiment one, its difference lies in：
Step（1）In, raw material phenol is heated to 120 DEG C through phenol preheater 1；Control 2 top pressure of phenol vaporizer
For 0.20MPaG；The admixture of gas being made of in raw material superheater 3 phenol and decarburization hydrogen is superheated to 175 DEG C；Phenol
Molar ratio with hydrogen is 1:2, the molar ratio of hydrogen and nitrogen is 5:1；Wherein in the preparation process of decarburization hydrogen：By oxidation of coal
Compound content is that the raw hydrogen of 20ppm is heated to temperature after hydrogen preheater 4 is preheated to 160 DEG C, then through hydrogen heater 5
To be sent into decarburizing reaction device 8 after 230 DEG C；Decarburizing reaction temperature control is 235 DEG C, and pressure control is 1.1MPaG.
Step（2）In, the reaction mass temperature control in hydrogenation reactor 6 is 195 DEG C, and pressure control is 0.1MPaG.
Step（3）In, hydrogenation reaction product carries out hot friendship with decarburization hydrogen in hydrogenation reactor heat recovering heat exchanger 7
Change, hydrogenation reaction product temperature is down to 105 DEG C.
Step（4）In, it is 0.05MPaG by the tower top pressure control of dehydrogenation tower 9, the bottom of towe of dehydrogenation tower 9 obtains temperature as 95
DEG C cyclohexanone crude product.Wherein gas is sent into recycling hydrogen gas compressor 13 by boost in pressure to 0.2MPaG；Control discharge system
Gas flow be 0.005 mol% of recycling hydrogen total amount, it is anti-to maintain to enter hydrogenation to give off the gas flow of system by control
Answer the gaseous impurity of device 6（Methane etc.）Content be 4 mol%.
Using this process, it is from the parameter of materials of 9 bottom of towe of dehydrogenation tower extraction finally：
Temperature：95℃；
Pressure：0.05MPaG
Composition：Cyclohexanone：90wt%, water：0.2wt%, cyclohexanol：7.6wt%, phenol：1.4wt%, light component:0.35wt%,
Heavy constituent：0.45wt%.
Specific embodiment three
With above-described embodiment one, its difference lies in：
Step（1）In, raw material phenol is heated to 140 DEG C through phenol preheater 1；Control 2 top pressure of phenol vaporizer
For 0.25MPaG；The admixture of gas being made of in raw material superheater 3 phenol and decarburization hydrogen is superheated to 195 DEG C；Phenol
Molar ratio with hydrogen is 1:6, the molar ratio of hydrogen and nitrogen is 2:1；Wherein in the preparation process of decarburization hydrogen：By carbon content
Temperature is heated to as 240 DEG C after hydrogen preheater 4 is preheated to 170 DEG C, then through hydrogen heater 5 for the raw hydrogen of 30ppm
Decarburizing reaction device 8 is sent into afterwards；Decarburizing reaction temperature control is 245 DEG C, and pressure control is 1.3MPaG.
Step（2）In, it is 180 DEG C by the reaction mass temperature control in hydrogenation reactor 6, pressure control is 0.2MPaG.
Step（3）In, hydrogenation reaction product carries out hot friendship with decarburization hydrogen in hydrogenation reactor heat recovering heat exchanger 7
Change, hydrogenation reaction product temperature is down to 115 DEG C.
Step（4）In, it is 0.15MPaG by the tower top pressure control of dehydrogenation tower 9, the bottom of towe of dehydrogenation tower 9 obtains temperature and is
105 DEG C of cyclohexanone crude product.Gas is sent into recycling hydrogen gas compressor 13 by boost in pressure to 0.3MPaG；Control discharge system
Gas flow be 0.01 mol% of recycling hydrogen total amount, it is anti-to maintain to enter hydrogenation to give off the gas flow of system by control
Answer the gaseous impurity of device 6（Methane etc.）Content be 1 mol%.
Using the method, it is from the parameter of materials of 9 bottom of towe of dehydrogenation tower extraction finally：
Temperature：105℃；
Pressure：0.15MPaG
Composition：Cyclohexanone：90.1wt%, water：0.2wt%, cyclohexanol：7.5wt%, phenol：1.4wt%, light component:
0.38wt%, heavy constituent：0.42wt%.
Specific embodiment four
The system of a kind of phenol production cyclohexanone method for above-mentioned specific embodiment one, as shown in Figure 1, including phenol
Preheater 1, phenol vaporizer 2, raw material superheater 3, hydrogen preheater 4, hydrogen heater 5, hydrogenation reactor 6, hydrogenation reaction
Device heat recovering heat exchanger 7, decarburizing reaction device 8 and dehydrogenation tower 9, phenol preheater 1 and the sidepiece feed inlet of phenol vaporizer 2 connect
Connect, the top discharge mouth of phenol vaporizer 2 is connected with the import of raw material superheater 3, the outlet of raw material superheater 3 and hydrogenation reaction
Its top feed mouth connection of device 6, the bottom discharge mouth of hydrogenation reactor 6 connect with the import of hydrogenation reactor heat recovering heat exchanger 7
Connecing, the outlet of hydrogenation reactor heat recovering heat exchanger 7 is connected with the lower end feed inlet of dehydrogenation tower 9, one end of hydrogen preheater 4,
Hydrogen heater 5, decarburizing reaction device 8 and the other end of hydrogen preheater 4 are in turn connected to form circulation loop, hydrogen preheater 4
It is connected by hydrogenation reactor heat recovering heat exchanger 7 with the lower end air inlet of phenol vaporizer 2, the bottom of dehydrogenation tower 9 is provided with
Cyclohexanone 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 for pushing up condenser 11 is connected by overhead reflux pump 12 with the upper end refluxing opening of dehydrogenation tower 9, the first overhead condenser
11 gaseous phase outlet, which is connected with, recycles hydrogen gas compressor 13, recycling the second overhead condenser 14 of connection of hydrogen gas compressor 13, and second
The liquid-phase outlet of overhead condenser 14 is connected by overhead reflux pump 12 with the upper end import of dehydrogenation tower 9, the second overhead condenser
14 gaseous phase outlet 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 vaporizer 2 is interior and is located at phenol vaporizer 2
The lower horizontal of sidepiece feed inlet 15 be provided with dismountable tubing heat exchanger 16, the barrel upper water of phenol vaporizer 2
It is flat to be provided with hydrogen inlet supervisor 17, the center in 2 cylinder of phenol vaporizer, hydrogen inlet master are extended in hydrogen inlet supervisor 17
The end of pipe 17 is connected with four longitudinally disposed and equally distributed hydrogen delivery branch pipes 18, and the lower section of hydrogen delivery branch pipe 18 is set
Be equipped with a horizontal circle Hydrogen distribution device 19, the ends of four hydrogen delivery branch pipes 18 respectively with circular Hydrogen distribution device 19
Connection, circular Hydrogen distribution device 19 be located at the lower section of tubing heat exchanger 16, Hydrogen distribution device 19 including be coaxially disposed it is interior in
Outer 3 ring shape Hydrogen distribution pipe 20, is both provided with several hydrogen dispersion holes 21 on each annular Hydrogen distribution pipe 20.
Certainly, described above is not limitation of the present invention, and the present invention is also not limited to the example above.The art
The variations, modifications, additions or substitutions that those of ordinary skill makes in the essential scope of the present invention, should also belong to protection of the present invention
Scope.
Claims (9)
- A kind of 1. method of phenol production cyclohexanone, it is characterised in that comprise the following steps：Raw material phenol is sent into phenol vaporizer after phenol preheater is heated to 120-140 DEG C, in phenol vaporizer, control Phenol vaporizer top pressure is 0.2-0.25MPaG, and phenol is heated double action, phenol vapour by decarburization hydrogen partial pressure and steam Formation gas is mixed with decarburization hydrogen and is sent into raw material superheater, is made of in raw material superheater phenol and decarburization hydrogen Admixture of gas is sent into hydrogenation reactor after being superheated to 175-195 DEG C of activation, and controls the gas into hydrogenation reactor to mix The molar ratio of phenol and hydrogen is 1 in compound:2-1:6；The preparation process flow of the wherein described decarburization hydrogen is：By oxidation of coal Compound content is that the raw hydrogen of 20-30ppm heats after hydrogen preheater is preheated to 160-170 DEG C, then through hydrogen heater Insulation fix bed formula decarburizing reaction device is sent into after being 230-240 DEG C to temperature；Removed in decarburizing reaction device in raw hydrogen Carbon monoxide and carbon dioxide, decarburizing reaction use Al2O3For the Ni catalyst of carrier, decarburizing reaction temperature control is 235-245 DEG C, pressure control is 1.1-1.3MPaG, and carbon monoxide is obtained after carbonization treatment and concentration of total carbon dioxide is less than the decarburization of 2ppb Hydrogen, send decarburization hydrogen into hydrogen preheater, and raw hydrogen carries out heat exchange, cooling with decarburization hydrogen in hydrogen preheater Phenol vaporizer is sent into after the hydrogenated reactor heat recovering heat exchanger heating of decarburization hydrogen afterwards；(2) it is 180-195 DEG C by the reaction temperature control of hydrogenation reactor, pressure control is 0.1-0.2MPaG, in hydrogenation reaction Phenol hydrogenation generates cyclohexanone in device, and is calandria type fixed bed etc. with generation by-product cyclic hexanol, wherein hydrogenation reactor Warm reactor, calandria type fixed bed isothermal reactor is interior to be equipped with Al2O3For the Pd catalyst of carrier；(3) hydrogenation reaction product is sent into hydrogenation reactor heat recovering heat exchanger from hydrogenation reactor bottom, in hydrogenation reaction Hydrogenation reaction product carries out heat exchange with decarburization hydrogen in device heat recovering heat exchanger, and the decarburization hydrogen after heating is sent into phenol vaporization Device, is cooled to 105-115 DEG C of hydrogenation reaction product and is sent into dehydrogenation tower；(4) it is 0.05-0.15MPaG by the tower top pressure control of dehydrogenation tower, hydrogenation reaction product is separated, dehydrogenation tower Tower top obtains unreacted hydrogen, and the bottom of towe of dehydrogenation tower obtains the cyclohexanone crude product that temperature is 95-105 DEG C.
- 2. the method for phenol production cyclohexanone according to claim 1, it is characterised in that：The tower of dehydrogenation tower in step (4) Top gas is mutually after the first overhead condenser is cooled to 40 DEG C through gas-liquid separation, and the liquid after separation is through overhead reflux pumped back dehydrogenation Top of tower as reflux, gas be sent into recycling hydrogen gas compressor by after boost in pressure to 0.2-0.3MPaG through the second overhead condensation Device cools down and through gas-liquid separation, and the liquid after separation sends dehydrogenation top of tower back to, and gas largely change by hydrogenated reactor recuperation of heat Phenol vaporizer, remaining small part discharge system are sent into after hot device heat temperature raising.
- 3. the method for phenol production cyclohexanone according to claim 2, it is characterised in that：Control the gas flow of discharge system To recycle the 0.005-0.01mol% of hydrogen total amount.
- 4. the method for phenol production cyclohexanone according to claim 1, it is characterised in that the entrance described in step (1) adds The control of the molar ratio of hydrogen and nitrogen is 5 in the admixture of gas of hydrogen reactor:1-2:1.
- 5. the method for phenol production cyclohexanone according to claim 1, it is characterised in that：The hydrogenation reactor is divided into Upper reaction section and lower part cooling section, the hydrogenation reactor are sent into hydrogenation reactor shell-side with boiler feedwater and produce 0.2- The saturated vapor of 0.3MPaG.
- 6. the system of a kind of method of phenol production cyclohexanone for described in claim 1, it is characterised in that：It is pre- including phenol Hot device, phenol vaporizer, raw material superheater, hydrogen preheater, hydrogen heater, hydrogenation reactor, hydrogenation reactor recuperation of heat Heat exchanger, decarburizing reaction device and dehydrogenation tower, the phenol preheater are connected with the sidepiece feed inlet of the phenol vaporizer, The top discharge mouth of the phenol vaporizer is connected with the import of the raw material superheater, and the raw material superheater goes out Mouth is connected with its top feed mouth of the hydrogenation reactor, the bottom discharge mouth of the hydrogenation reactor and the hydrogenation The import connection of reactor heat recovering heat exchanger, outlet and the dehydrogenation tower of the hydrogenation reactor heat recovering heat exchanger The connection of lower end feed inlet, one end of the hydrogen preheater, the hydrogen heater, the decarburizing reaction device and institute The other end for the hydrogen preheater stated is in turn connected to form circulation loop, and the hydrogen preheater passes through the hydrogenation reaction Device recuperation of heat reactor is connected with the lower end air inlet of the phenol vaporizer, and the bottom of the dehydrogenation tower is provided with hexamethylene Ketone product outlet.
- 7. the system of phenol production cyclohexanone according to claim 6, it is characterised in that：The top gas of the dehydrogenation tower Phase exit is provided with the first overhead condenser, and the liquid-phase outlet of first overhead condenser is pumped by overhead reflux and institute The upper end import connection for the dehydrogenation tower stated, the gaseous phase outlet of first overhead condenser are connected with recycling hydrogen gas compressor, The recycling hydrogen gas compressor connects the second overhead condenser, and the liquid-phase outlet of second overhead condenser passes through tower top Reflux pump is connected with the upper end import of the dehydrogenation tower, the gaseous phase outlet of second overhead condenser and the hydrogenation Reactor heat recovering heat exchanger connects.
- 8. the system of phenol production cyclohexanone according to claim 6, it is characterised in that：The dehydrogenation tower is board-like steaming Tower is evaporated, column plate can be float valve or sieve plate, and the number of plates is 5-10 layers.
- 9. the system of phenol production cyclohexanone according to claim 6, it is characterised in that：The cylinder of the phenol vaporizer The lower horizontal of sidepiece feed inlet in vivo and positioned at the phenol vaporizer is provided with dismountable tubing heat exchanger, institute The barrel upper level for the phenol vaporizer stated is provided with hydrogen inlet supervisor, is extended in hydrogen inlet supervisor in cylinder Center, the hydrogen inlet supervisor end be connected with four longitudinally disposed and equally distributed hydrogen delivery branch pipes, institute A horizontal circle Hydrogen distribution device is provided with below the hydrogen delivery branch pipe stated, the hydrogen delivery branch pipe described in four End is connected with the circular Hydrogen distribution device respectively, and the circular Hydrogen distribution device is located at the tubing heat exchanger Lower section, the circular Hydrogen distribution device includes the inside and outside 3 ring shape Hydrogen distribution pipe that is coaxially disposed, each ring Several hydrogen dispersion holes are both provided with shape Hydrogen distribution pipe.
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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 |
-
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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