CN104402694B - A kind of cyclohexane liquid-phase oxidation legal system is for the method for pimelinketone - Google Patents
A kind of cyclohexane liquid-phase oxidation legal system is for the method for pimelinketone Download PDFInfo
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- CN104402694B CN104402694B CN201410552769.4A CN201410552769A CN104402694B CN 104402694 B CN104402694 B CN 104402694B CN 201410552769 A CN201410552769 A CN 201410552769A CN 104402694 B CN104402694 B CN 104402694B
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- C—CHEMISTRY; METALLURGY
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- 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
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention discloses the method for a kind of cyclohexane liquid-phase oxidation legal system for pimelinketone, from cyclohexane oxidation alcohol ketone out successively through the first rectifying tower separating ring hexanone product, after Second distillation column and the 3rd rectifying tower isolate cyclohexanol, the hexalin that separation obtains is added dehydrogenation reactor through alcohol groove and carries out dehydrogenation reaction, dehydrogenation reactor reaction product is out entered successively the component of the 4th rectifying tower separation of C less than 6, after 5th rectifying tower rectifying separation pimelinketone product, using the charging of the 5th tower bottom of rectifying tower liquid circulation as Second distillation column, a light constituent tripping device is set after the 5th rectifying tower, the high raw material of light constituent content is made to be able to remove in advance in light constituent tripping device, thus light constituent content in reduction hexalin.The present invention has that technique is simple, cost is low, the advantage of light constituent good separating effect.
Description
Technical field
The invention belongs to petrochemical industry field of new, be specifically related to the method for a kind of cyclohexane liquid-phase oxidation legal system for pimelinketone.
Background technology
Pimelinketone is a kind of important Organic chemical products, has high resolution and low volatility, can as special solvent, to polymkeric substance if nitro-cotton and Mierocrystalline cellulose etc. are a kind of desirable solvents.Pimelinketone is also important Organic Chemicals, still prepares the main intermediate of hexanolactam and hexanodioic acid.Pimelinketone industrial manufacture process mainly contains phenol hydrogenation method, cyclohexane liquid-phase oxidation method, cyclohexene hydration method in the world.Wherein, cyclohexane liquid-phase oxidation method is because of technical maturity, starting raw material benzene abundance, and quality product quality better is the main method of current industrial production pimelinketone.
Cyclohexane liquid-phase oxidation legal system is for the production technique of pimelinketone, and be with benzene and hydrogen for raw material, hydrogenation generates hexanaphthene; Hexanaphthene generates pimelinketone and hexalin through atmospheric oxidation, decomposition saponification again; The hexalin separated obtains pimelinketone through dehydrogenation again.In cyclohexane liquid-phase oxidation legal system in the production technique of pimelinketone, the side reaction in atmospheric oxidation generation pimelinketone and hexalin and follow-up decomposition reaction of main reaction hexanaphthene is many and assorted.The butylcyclohexyl ether (BCHE) wherein formed, the light constituent materials such as two cyclic group ethers are not easily from alcohol, separate in ketone, in actual production, they enter alcohol tower with thick hexalin, then be recovered as alcohol column overhead product, and enter cyclohexanol dehydrogenation device, at dehydrogenation gas-liquid separation tank bottom portion butylcyclohexyl ether, the concentration of the light constituent impurity such as two cyclic group ethers is increased and is back to alcohol tower, the circulative accumulation repeated, add the energy consumption of material when tower internal recycle and the working cost of device, have a strong impact on the purity of hexalin, and finally affect the quality of pimelinketone, even more serious consequence is that the light constituent impurity such as butylcyclohexyl ether (BCHE), two cyclic group ethers in thick hexalin can cause cyclohexanol dehydrogenation to prepare copper in pimelinketone Technology-zinc system co-precipitated catalyst inactivation, and copper-zinc system is shortened in the co-precipitated catalyst life-span greatly.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, provide that a kind of technique is simple, cost is low, the cyclohexane liquid-phase oxidation legal system of light constituent good separating effect is for the method for pimelinketone.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of cyclohexane liquid-phase oxidation legal system is for the method for pimelinketone, from cyclohexane oxidation alcohol ketone out successively through the first rectifying tower separating ring hexanone product, after Second distillation column and the 3rd rectifying tower isolate cyclohexanol, the hexalin that separation obtains is added dehydrogenation reactor through alcohol groove and carries out dehydrogenation reaction, dehydrogenation reactor reaction product is out entered successively the component of the 4th rectifying tower separation of C less than 6, after 5th rectifying tower rectifying separation pimelinketone product, using the charging of the 5th tower bottom of rectifying tower liquid circulation as Second distillation column, a light constituent tripping device is set after the 5th rectifying tower, described light constituent tripping device comprises light constituent knockout tower and intermediate storage tank, the tower top discharge nozzle of described light constituent knockout tower is connected with alcohol groove opening for feed with described intermediate storage tank opening for feed with the second trip valve respectively by the first trip valve, the 5th described tower bottom of rectifying tower discharge port is connected with light constituent knockout tower feed-pipe with described Second distillation column feed-pipe with the 3rd trip valve respectively by the 7th trip valve, the tower reactor discharge nozzle of described light constituent knockout tower is connected by the 6th trip valve with the opening for feed of described Second distillation column, the tower reactor discharge nozzle of described light constituent knockout tower is provided with discharging arm, described discharging arm is provided with the 5th trip valve, described intermediate storage tank discharge nozzle is connected by the 4th trip valve with the opening for feed of described light constituent knockout tower,
When in the 5th tower bottom of rectifying tower liquid, light constituent mass percentage reaches 4.5 ~ 8%, open the 3rd trip valve, the first trip valve, the 6th trip valve, close the 4th trip valve, the second trip valve, the 5th trip valve, by regulating the 7th trip valve inlet flow rate and light constituent knockout tower feed rate, the tower bottoms of 30 ~ 70% is entered light constituent knockout tower and be separated light constituent, obtain tower top light constituent and light constituent knockout tower tower bottoms, tower top light constituent is collected intermediate storage tank, using the charging of light constituent knockout tower tower bottoms circulation as Second distillation column;
When intermediate storage tank is filled, close the first trip valve, the 6th trip valve, open the 4th trip valve, the second trip valve, the 5th trip valve, the material of intermediate storage tank is entered light constituent knockout tower and carries out rectifying, obtain light constituent knockout tower overhead fraction and light constituent knockout tower tower bottoms, light constituent knockout tower overhead fraction is recycled to alcohol groove, light constituent knockout tower tower bottoms is collected by the 5th trip valve.
As the preferred embodiments of the invention, the 5th tower bottom of rectifying tower liquid of 30 ~ 70% being entered the operational condition of light constituent knockout tower when light constituent knockout tower is separated light constituent is: tower top pressure 1.7 ~ 2.3Kpa, bottom temperature 88 ~ 95 DEG C, reflux ratio 1.3 ~ 1.8m
3/ h.
As the preferred embodiments of the invention, the operational condition entering light constituent knockout tower when light constituent knockout tower carries out rectifying when the material of intermediate storage tank is: tower top pressure 65 ~ 75Kpa, bottom temperature 150 ~ 170 DEG C, reflux ratio 3 ~ 4m
3/ h.
As the preferred embodiments of the invention, preferably the 5th tower bottom of rectifying tower liquid of 40 ~ 60% is entered light constituent knockout tower and be separated light constituent.
Cyclohexane liquid-phase oxidation legal system of the present invention, for the method for pimelinketone, by light constituent tripping device, makes the high material of light constituent content be able to remove charging more in advance in light constituent knockout tower, thus reduces light constituent content in hexalin.Meanwhile, light constituent knockout tower one tower multipotency, after can realizing the enrichment of high density light constituent cut, then removes, reduces energy consumption with this.Final realization extends cyclohexanol dehydrogenation and prepares copper in pimelinketone technique-zinc system co-precipitated catalyst life-span, simultaneously enhancing ring hexanone quality product and then lifting caprolactam product quality.
Advantage of the present invention is:
1, technique is simple, cost is low, light constituent knockout tower one tower multipotency, can apply in a flexible way, the light constituents such as butylcyclohexyl ether (BCHE), two cyclic group ethers first concentrate by the first step, and second step takes off ether, removes the ether material produced in cyclohexane oxidation process, decrease the energy consumption of material when tower internal recycle, while reaching Improving The Quality of Products, save running cost, decreased working cost;
2, light constituent good separating effect, removal efficiency is high, in the rear light constituent knockout tower tower bottoms of process, the light constituent content such as butylcyclohexyl ether (BCHE), two cyclic group ethers is more than 98%, in overhead fraction, the light constituent content such as butylcyclohexyl ether (BCHE), two cyclic group ethers is below 0.5%, light constituent after process can be recycled;
3, improve plant running cycle and quality product, the separation of light constituent in hexalin, extend cyclohexanol dehydrogenation and prepare copper in pimelinketone technique-zinc system co-precipitated catalyst life-span, improve pimelinketone quality product simultaneously, pimelinketone product purity is more than 99.97%, in pimelinketone product, methyl-n-butyl ketone and hexanal total content are at below 30ppm, 2-heptanone content is at below 25ppm, valeral content is at below 5ppm, hexalin content is at below 40ppm, alcohol content is at below 26ppm, and total methylcyclohexanone content, at below 75ppm, reaches top grade product index.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
As shown in the figure: 1 is the first rectifying tower, 2 is Second distillation column, and 3 is the 3rd rectifying tower, 4 is alcohol groove, and 5 is dehydrogenation reactor, and 6 be the 4th rectifying tower, 7 is the 5th rectifying tower, 8 is light constituent knockout tower, and 9 is intermediate storage tank, and 10 is the first trip valve, 11 is the second trip valve, 12 is the 3rd trip valve, and 13 is the 4th trip valve, and 14 is the 5th trip valve, 15 is the 6th trip valve, and 16 is the 7th trip valve.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
As shown in Figure 1, cyclohexane liquid-phase oxidation legal system of the present invention is for the method for pimelinketone, from cyclohexane oxidation alcohol ketone out successively through the first rectifying tower 1 separating ring hexanone product, after Second distillation column 2 and the 3rd rectifying tower 3 isolate cyclohexanol, overhead fraction hexalin and tower reactor by-product X oil production is obtained from the 3rd rectifying tower 3, the hexalin that separation obtains is added dehydrogenation reactor 5 through alcohol groove 4 and carries out dehydrogenation reaction, dehydrogenation reactor 5 reaction product is out entered successively the component of the 4th rectifying tower 6 separation of C less than 6, after 5th rectifying tower 7 rectifying separation pimelinketone product, using the charging of the 5th rectifying tower 7 tower bottoms circulation as Second distillation column 2, a light constituent tripping device is set after the 5th rectifying tower 7, described light constituent tripping device comprises light constituent knockout tower 8 and intermediate storage tank 9, the tower top discharge nozzle of described light constituent knockout tower 8 is connected with alcohol groove 4 opening for feed with described intermediate storage tank 9 opening for feed with the second trip valve 11 respectively by the first trip valve 10, the 5th described rectifying tower 7 tower reactor discharge port is connected with light constituent knockout tower 8 feed-pipe with described Second distillation column 2 feed-pipe with the 3rd trip valve 12 respectively by the 7th trip valve 16, the tower reactor discharge nozzle of described light constituent knockout tower 8 is provided with discharging arm, described discharging arm is provided with the 5th trip valve 14, described intermediate storage tank 9 discharge nozzle is connected by the 4th trip valve 13 with the opening for feed of described light constituent knockout tower 8, the 7th described trip valve 16 entrance and light constituent knockout tower 8 import are provided with under meter.
When in the 5th rectifying tower 7 tower bottoms, light constituent mass percentage reaches 4.5 ~ 8%, open the 3rd trip valve 12, first trip valve 10, the 6th trip valve 15, close the 4th trip valve 13, second trip valve 11, the 5th trip valve 14, the tower bottoms of 30 ~ 70% of the 5th rectifying tower 7 is entered light constituent knockout tower 8 and is separated light constituent, obtain tower top light constituent and light constituent knockout tower 8 tower bottoms, tower top light constituent is collected intermediate storage tank 9, using the charging of light constituent knockout tower 8 tower bottoms circulation as Second distillation column 2;
When intermediate storage tank 9 is filled, close the first trip valve 10, the 6th trip valve 15, open the 4th trip valve 13, second trip valve 11, the 5th trip valve 14, the material of intermediate storage tank 9 is entered light constituent knockout tower 8 and carry out rectifying, obtain light constituent knockout tower 8 overhead fraction and light constituent knockout tower 8 tower bottoms, light constituent knockout tower 8 overhead fraction is recycled to alcohol groove 4, light constituent knockout tower 8 tower bottoms is collected by the 5th trip valve 14.
Embodiment 1
From cyclohexane oxidation alcohol ketone out successively through the first rectifying tower 1 separating ring hexanone product, after Second distillation column 2 and the 3rd rectifying tower 3 isolate cyclohexanol, overhead fraction hexalin and tower reactor by-product X oil production is obtained from the 3rd rectifying tower 3, the hexalin that separation obtains is added dehydrogenation reactor 5 through alcohol groove 4 and carries out dehydrogenation reaction, dehydrogenation reactor 5 reaction product is out entered successively the component of the 4th rectifying tower 6 separation of C less than 6, after 5th rectifying tower 7 rectifying separation pimelinketone product, by the 7th trip valve often opened, the 5th rectifying tower 7 tower bottoms is circulated as the charging of Second distillation column 2, when in the 5th rectifying tower 7 tower bottoms, light constituent mass percentage reaches 4.5%, open the 3rd trip valve 12, first trip valve 10, 6th trip valve 15, close the 4th trip valve 13, second trip valve 11, 5th trip valve 14, take into account light constituent knockout tower 8 feed flow meter by regulating the 7th trip valve 16 inlet flow rate and the tower bottoms of 30% is entered light constituent knockout tower 8 (Ф 1000X27252, stuffing rectification column, carbon steel) be separated light constituent, the operational condition of light constituent knockout tower 8 is: tower top pressure 1.8Kpa, bottom temperature 90 DEG C, reflux ratio 1.5m
3/ h, obtains tower top light constituent and tower bottoms, tower top light constituent is collected intermediate storage tank 9 (Ф 13000X7710, V=50m
3', carbon steel), using the charging of tower bottoms circulation as Second distillation column 2.When intermediate storage tank 9 is filled, close the first trip valve 10, the 6th trip valve 15, open the 4th trip valve 13, second trip valve 11, the 5th trip valve 14, the material of intermediate storage tank 9 is also entered light constituent knockout tower 8 and carry out rectifying, now the operational condition of light constituent knockout tower 8 is: tower top pressure 65Kpa, bottom temperature 150 DEG C, reflux ratio 3m
3/ h, obtain overhead fraction and tower bottoms, overhead fraction is recycled to alcohol groove and sampling analysis, tower bottoms is collected and sampling analysis by the 5th trip valve 14, in overhead fraction, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 0.5%, and in tower bottoms, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 98%.Collect pimelinketone product sampling analysis that the 5th rectifying tower 7 tower top obtains, pimelinketone product purity 99.97%, methyl-n-butyl ketone and hexanal content are 30ppm, 2-heptanone content is 25ppm, valeral content is 5ppm, hexalin content is 40ppm, alcohol content is 20ppm, and total methylcyclohexanone content is 70ppm.All reach top grade product index.Embodiment 2
From cyclohexane oxidation alcohol ketone out successively through the first rectifying tower 1 separating ring hexanone product, after Second distillation column 2 and the 3rd rectifying tower 3 isolate cyclohexanol, overhead fraction hexalin and tower reactor by-product X oil production is obtained from the 3rd rectifying tower 3, the hexalin that separation obtains is added dehydrogenation reactor 5 through alcohol groove 4 and carries out dehydrogenation reaction, dehydrogenation reactor 5 reaction product is out entered successively the component of the 4th rectifying tower 6 separation of C less than 6, after 5th rectifying tower 7 rectifying separation pimelinketone product, by the 7th trip valve often opened, the 5th rectifying tower 7 tower bottoms is circulated as the charging of Second distillation column 2, when in the 5th rectifying tower 7 tower bottoms, light constituent mass percentage reaches 5%, open the 3rd trip valve 12, first trip valve 10, 6th trip valve 15, close the 4th trip valve 13, second trip valve 11, 5th trip valve 14, take into account light constituent knockout tower 8 feed flow meter by regulating the 7th trip valve 16 inlet flow rate and the tower bottoms of 40% is entered light constituent knockout tower 8 (Ф 1000X27252, stuffing rectification column, carbon steel) be separated light constituent, the operational condition of light constituent knockout tower 8 is: tower top pressure 2.0Kpa, bottom temperature 93 DEG C, reflux ratio 1.3m
3/ h, obtains tower top light constituent and tower bottoms, tower top light constituent is collected intermediate storage tank 9 (Ф 13000X7710, V=50m
3', carbon steel), using the charging of tower bottoms circulation as Second distillation column 2.When intermediate storage tank 9 is filled, close the first trip valve 10, the 6th trip valve 15, open the 4th trip valve 13, second trip valve 11, the 5th trip valve 14, the material of intermediate storage tank 9 is also entered light constituent knockout tower 8 and carry out rectifying, now the operational condition of light constituent knockout tower 8 is: tower top pressure 65Kpa, bottom temperature 155 DEG C, reflux ratio 3m
3/ h, obtain overhead fraction and tower bottoms, overhead fraction is recycled to alcohol groove and sampling analysis, tower bottoms is collected and sampling analysis by the 5th trip valve 14, in overhead fraction, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 0.4%, and in tower bottoms, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 98.5%.Collect pimelinketone product sampling analysis that the 5th rectifying tower 7 tower top obtains, pimelinketone product purity 99.98%, methyl-n-butyl ketone and hexanal content are 28ppm, 2-heptanone content is 25ppm, valeral content is 4ppm, hexalin content is 30ppm, alcohol content is 18ppm, and total methylcyclohexanone content is 50ppm.All reach top grade product index.
Embodiment 3
From cyclohexane oxidation alcohol ketone out successively through the first rectifying tower 1 separating ring hexanone product, after Second distillation column 2 and the 3rd rectifying tower 3 isolate cyclohexanol, overhead fraction hexalin and tower reactor by-product X oil production is obtained from the 3rd rectifying tower 3, the hexalin that separation obtains is added dehydrogenation reactor 5 through alcohol groove 4 and carries out dehydrogenation reaction, dehydrogenation reactor 5 reaction product is out entered successively the component of the 4th rectifying tower 6 separation of C less than 6, after 5th rectifying tower 7 rectifying separation pimelinketone product, by the 7th trip valve often opened, the 5th rectifying tower 7 tower bottoms is circulated as the charging of Second distillation column 2, when in the 5th rectifying tower 7 tower bottoms, light constituent mass percentage reaches 5.5%, open the 3rd trip valve 12, first trip valve 10, 6th trip valve 15, close the 4th trip valve 13, second trip valve 11, 5th trip valve 14, take into account light constituent knockout tower 8 feed flow meter by regulating the 7th trip valve 16 inlet flow rate and the tower bottoms of 40% is entered light constituent knockout tower 8 (Ф 1000X27252, stuffing rectification column, carbon steel) be separated light constituent, the operational condition of light constituent knockout tower 8 is: tower top pressure 2.3Kpa, bottom temperature 93 DEG C, reflux ratio 1.8m
3/ h, obtains tower top light constituent and tower bottoms, tower top light constituent is collected intermediate storage tank 9 (Ф 13000X7710, V=50m
3', carbon steel), using the charging of tower bottoms circulation as Second distillation column 2.When intermediate storage tank 9 is filled, close the first trip valve 10, the 6th trip valve 15, open the 4th trip valve 13, second trip valve 11, the 5th trip valve 14, the material of intermediate storage tank 9 is also entered light constituent knockout tower 8 and carry out rectifying, now the operational condition of light constituent knockout tower 8 is: tower top pressure 70Kpa, bottom temperature 160 DEG C, reflux ratio 3m
3/ h, obtain overhead fraction and tower bottoms, overhead fraction is recycled to alcohol groove and sampling analysis, tower bottoms is collected and sampling analysis by the 5th trip valve 14, in overhead fraction, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 0.3%, and in tower bottoms, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 98.7%.Collect pimelinketone product sampling analysis that the 5th rectifying tower 7 tower top obtains, pimelinketone product purity 99.98%, methyl-n-butyl ketone and hexanal content are 26ppm, 2-heptanone content is 23ppm, valeral content is 5ppm, hexalin content is 25ppm, alcohol content is 26ppm, and total methylcyclohexanone content is 65ppm.All reach top grade product index.
Embodiment 4
From cyclohexane oxidation alcohol ketone out successively through the first rectifying tower 1 separating ring hexanone product, after Second distillation column 2 and the 3rd rectifying tower 3 isolate cyclohexanol, overhead fraction hexalin and tower reactor by-product X oil production is obtained from the 3rd rectifying tower 3, the hexalin that separation obtains is added dehydrogenation reactor 5 through alcohol groove 4 and carries out dehydrogenation reaction, dehydrogenation reactor 5 reaction product is out entered successively the component of the 4th rectifying tower 6 separation of C less than 6, after 5th rectifying tower 7 rectifying separation pimelinketone product, by the 7th trip valve often opened, the 5th rectifying tower 7 tower bottoms is circulated as the charging of Second distillation column 2, when in the 5th rectifying tower 7 tower bottoms, light constituent mass percentage reaches 6.0%, open the 3rd trip valve 12, first trip valve 10, 6th trip valve 15, close the 4th trip valve 13, second trip valve 11, 5th trip valve 14, take into account light constituent knockout tower 8 feed flow meter by regulating the 7th trip valve 16 inlet flow rate and the tower bottoms of 50% is entered light constituent knockout tower 8 (Ф 1000X27252, stuffing rectification column, carbon steel) be separated light constituent, the operational condition of light constituent knockout tower 8 is: tower top pressure 1.7Kpa, bottom temperature 92 DEG C, reflux ratio 1.65m
3/ h, obtains tower top light constituent and tower bottoms, tower top light constituent is collected intermediate storage tank 9 (Ф 13000X7710, V=50m
3', carbon steel), using the charging of tower bottoms circulation as Second distillation column 2.When intermediate storage tank 9 is filled, close the first trip valve 10, the 6th trip valve 15, open the 4th trip valve 13, second trip valve 11, the 5th trip valve 14, the material of intermediate storage tank 9 is also entered light constituent knockout tower 8 and carry out rectifying, now the operational condition of light constituent knockout tower 8 is: tower top pressure 70Kpa, bottom temperature 160 DEG C, reflux ratio 3.5m
3/ h, obtain overhead fraction and tower bottoms, overhead fraction is recycled to alcohol groove and sampling analysis, tower bottoms is collected and sampling analysis by the 5th trip valve 14, in overhead fraction, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 0.2%, and in tower bottoms, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 98.9%.Collect pimelinketone product sampling analysis that the 5th rectifying tower 7 tower top obtains, pimelinketone product purity 99.97%, methyl-n-butyl ketone and hexanal content are 24ppm, 2-heptanone content is 22ppm, valeral content is 4ppm, hexalin content is 30ppm, alcohol content is 19ppm, and total methylcyclohexanone content is 70ppm.All reach top grade product index.
Embodiment 5
From cyclohexane oxidation alcohol ketone out successively through the first rectifying tower 1 separating ring hexanone product, after Second distillation column 2 and the 3rd rectifying tower 3 isolate cyclohexanol, overhead fraction hexalin and tower reactor by-product X oil production is obtained from the 3rd rectifying tower 3, the hexalin that separation obtains is added dehydrogenation reactor 5 through alcohol groove 4 and carries out dehydrogenation reaction, dehydrogenation reactor 5 reaction product is out entered successively the component of the 4th rectifying tower 6 separation of C less than 6, after 5th rectifying tower 7 rectifying separation pimelinketone product, by the 7th trip valve often opened, the 5th rectifying tower 7 tower bottoms is circulated as the charging of Second distillation column 2, when in the 5th rectifying tower 7 tower bottoms, light constituent mass percentage reaches 6.5%, open the 3rd trip valve 12, first trip valve 10, 6th trip valve 15, close the 4th trip valve 13, second trip valve 11, 5th trip valve 14, take into account light constituent knockout tower 8 feed flow meter by regulating the 7th trip valve 16 inlet flow rate and the tower bottoms of 60% is entered light constituent knockout tower 8 (Ф 1000X27252, stuffing rectification column, carbon steel) be separated light constituent, the operational condition of light constituent knockout tower 8 is: tower top pressure 2.3Kpa, bottom temperature 93 DEG C, reflux ratio 1.65m
3/ h, obtains tower top light constituent and tower bottoms, tower top light constituent is collected intermediate storage tank 9 (Ф 13000X7710, V=50m
3', carbon steel), using the charging of tower bottoms circulation as Second distillation column 2.When intermediate storage tank 9 is filled, close the first trip valve 10, the 6th trip valve 15, open the 4th trip valve 13, second trip valve 11, the 5th trip valve 14, the material of intermediate storage tank 9 is also entered light constituent knockout tower 8 and carry out rectifying, now the operational condition of light constituent knockout tower 8 is: tower top pressure 70Kpa, bottom temperature 165 DEG C, reflux ratio 3.5m
3/ h, obtain overhead fraction and tower bottoms, overhead fraction is recycled to alcohol groove and sampling analysis, tower bottoms is collected and sampling analysis by the 5th trip valve 14, in overhead fraction, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 0.4%, and in tower bottoms, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 98.3%.Collect pimelinketone product sampling analysis that the 5th rectifying tower 7 tower top obtains, pimelinketone product purity 99.97%, methyl-n-butyl ketone and hexanal content are 15ppm, 2-heptanone content is 24ppm, valeral content is 3ppm, hexalin content is 20ppm, alcohol content is 19ppm, and total methylcyclohexanone content is 65ppm.All reach top grade product index.
Embodiment 6
From cyclohexane oxidation alcohol ketone out successively through the first rectifying tower 1 separating ring hexanone product, after Second distillation column 2 and the 3rd rectifying tower 3 isolate cyclohexanol, overhead fraction hexalin and tower reactor by-product X oil production is obtained from the 3rd rectifying tower 3, the hexalin that separation obtains is added dehydrogenation reactor 5 through alcohol groove 4 and carries out dehydrogenation reaction, dehydrogenation reactor 5 reaction product is out entered successively the component of the 4th rectifying tower 6 separation of C less than 6, after 5th rectifying tower 7 rectifying separation pimelinketone product, by the 7th trip valve often opened, the 5th rectifying tower 7 tower bottoms is circulated as the charging of Second distillation column 2, when in the 5th rectifying tower 7 tower bottoms, light constituent mass percentage reaches 7.0%, open the 3rd trip valve 12, first trip valve 10, 6th trip valve 15, close the 4th trip valve 13, second trip valve 11, 5th trip valve 14, take into account light constituent knockout tower 8 feed flow meter by regulating the 7th trip valve 16 inlet flow rate and the tower bottoms of 60% is entered light constituent knockout tower 8 (Ф 1000X27252, stuffing rectification column, carbon steel) be separated light constituent, the operational condition of light constituent knockout tower 8 is: tower top pressure 2.2Kpa, bottom temperature 94 DEG C, reflux ratio 1.8m
3/ h, obtains tower top light constituent and tower bottoms, tower top light constituent is collected intermediate storage tank 9 (Ф 13000X7710, V=50m
3', carbon steel), using the charging of tower bottoms circulation as Second distillation column 2.When intermediate storage tank 9 is filled, close the first trip valve 10, the 6th trip valve 15, open the 4th trip valve 13, second trip valve 11, the 5th trip valve 14, the material of intermediate storage tank 9 is also entered light constituent knockout tower 8 and carry out rectifying, now the operational condition of light constituent knockout tower 8 is: tower top pressure 75Kpa, bottom temperature 165 DEG C, reflux ratio 4m
3/ h, obtain overhead fraction and tower bottoms, overhead fraction is recycled to alcohol groove and sampling analysis, tower bottoms is collected and sampling analysis by the 5th trip valve 14, in overhead fraction, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 0.3%, and in tower bottoms, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 98.9%.Collect pimelinketone product sampling analysis that the 5th rectifying tower 7 tower top obtains, pimelinketone product purity 99.98%, methyl-n-butyl ketone and hexanal content are 10ppm, 2-heptanone content is 15ppm, valeral content is 0ppm, hexalin content is 10ppm, alcohol content is 10ppm, and total methylcyclohexanone content is 40ppm.All reach top grade product index.
Embodiment 7
From cyclohexane oxidation alcohol ketone out successively through the first rectifying tower 1 separating ring hexanone product, after Second distillation column 2 and the 3rd rectifying tower 3 isolate cyclohexanol, overhead fraction hexalin and tower reactor by-product X oil production is obtained from the 3rd rectifying tower 3, the hexalin that separation obtains is added dehydrogenation reactor 5 through alcohol groove 4 and carries out dehydrogenation reaction, dehydrogenation reactor 5 reaction product is out entered successively the component of the 4th rectifying tower 6 separation of C less than 6, after 5th rectifying tower 7 rectifying separation pimelinketone product, by the 7th trip valve often opened, the 5th rectifying tower 7 tower bottoms is circulated as the charging of Second distillation column 2, when in the 5th rectifying tower 7 tower bottoms, light constituent mass percentage reaches 7.5%, open the 3rd trip valve 12, first trip valve 10, 6th trip valve 15, close the 4th trip valve 13, second trip valve 11, 5th trip valve 14, take into account light constituent knockout tower 8 feed flow meter by regulating the 7th trip valve 16 inlet flow rate and the tower bottoms of 70% is entered light constituent knockout tower 8 (Ф 1000X27252, stuffing rectification column, carbon steel) be separated light constituent, the operational condition of light constituent knockout tower 8 is: tower top pressure 1.9Kpa, bottom temperature 90 DEG C, reflux ratio 1.5m
3/ h, obtains tower top light constituent and tower bottoms, tower top light constituent is collected intermediate storage tank 9 (Ф 13000X7710, V=50m
3', carbon steel), using the charging of tower bottoms circulation as Second distillation column 2.When intermediate storage tank 9 is filled, close the first trip valve 10, the 6th trip valve 15, open the 4th trip valve 13, second trip valve 11, the 5th trip valve 14, the material of intermediate storage tank 9 is also entered light constituent knockout tower 8 and carry out rectifying, now the operational condition of light constituent knockout tower 8 is: tower top pressure 75Kpa, bottom temperature 170 DEG C, reflux ratio 4m
3/ h, obtain overhead fraction and tower bottoms, overhead fraction is recycled to alcohol groove and sampling analysis, tower bottoms is collected and sampling analysis by the 5th trip valve 14, in overhead fraction, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 0.2%, and in tower bottoms, the light constituent content such as cyclohexylbutyl ether (BCHE), two cyclic group ethers is 98.6%.Collect pimelinketone product sampling analysis that the 5th rectifying tower 7 tower top obtains, pimelinketone product purity 99.98%, methyl-n-butyl ketone and hexanal content are 18ppm, 2-heptanone content is 21ppm, valeral content is 2ppm, hexalin content is 14ppm, alcohol content is 17ppm, and total methylcyclohexanone content is 75ppm.All reach top grade product index.
Claims (2)
1. a cyclohexane liquid-phase oxidation legal system is for the method for pimelinketone, from cyclohexane oxidation alcohol ketone out successively through the first rectifying tower separating ring hexanone product, after Second distillation column and the 3rd rectifying tower isolate cyclohexanol, the hexalin that separation obtains is added dehydrogenation reactor through alcohol groove and carries out dehydrogenation reaction, dehydrogenation reactor reaction product is out entered successively the component of the 4th rectifying tower separation of C less than 6, after 5th rectifying tower rectifying separation pimelinketone product, using the charging of the 5th tower bottom of rectifying tower liquid circulation as Second distillation column, it is characterized in that arranging a light constituent tripping device after the 5th rectifying tower, described light constituent tripping device comprises light constituent knockout tower and intermediate storage tank, the tower top discharge nozzle of described light constituent knockout tower is connected with alcohol groove opening for feed with described intermediate storage tank opening for feed with the second trip valve respectively by the first trip valve, the 5th described tower bottom of rectifying tower discharge port is connected with light constituent knockout tower feed-pipe with described Second distillation column feed-pipe with the 3rd trip valve respectively by the 7th trip valve, the tower reactor discharge nozzle of described light constituent knockout tower is connected by the 6th trip valve with the opening for feed of described Second distillation column, the tower reactor discharge nozzle of described light constituent knockout tower is provided with discharging arm, described discharging arm is provided with the 5th trip valve, described intermediate storage tank discharge nozzle is connected by the 4th trip valve with the opening for feed of described light constituent knockout tower,
When in the 5th tower bottom of rectifying tower liquid, light constituent mass percentage reaches 4.5 ~ 8%, open the 3rd trip valve, the first trip valve, the 6th trip valve, close the 4th trip valve, the second trip valve, the 5th trip valve, by regulating the 7th trip valve inlet flow rate and light constituent knockout tower feed rate, the tower bottoms of 30 ~ 70% is entered light constituent knockout tower and be separated light constituent, now the operational condition of light constituent knockout tower is: tower top pressure 1.7 ~ 2.3KPa, bottom temperature 88 ~ 95 DEG C, reflux ratio 1.3 ~ 1.8m
3/ h, obtains tower top light constituent and light constituent knockout tower tower bottoms, tower top light constituent is collected intermediate storage tank, using the charging of light constituent knockout tower tower bottoms circulation as Second distillation column;
When intermediate storage tank is filled, close the first trip valve, the 6th trip valve, open the 4th trip valve, the second trip valve, the 5th trip valve, the material of intermediate storage tank is entered light constituent knockout tower and carries out rectifying, now the operational condition of light constituent knockout tower is: tower top pressure 65 ~ 75KPa, bottom temperature 150 ~ 170 DEG C, reflux ratio 3 ~ 4m
3/ h, obtains light constituent knockout tower overhead fraction and light constituent knockout tower tower bottoms, light constituent knockout tower overhead fraction is recycled to alcohol groove, is collected by light constituent knockout tower tower bottoms by the 5th trip valve.
2. cyclohexane liquid-phase oxidation legal system according to claim 1 is for the method for pimelinketone, it is characterized in that the 5th tower bottom of rectifying tower liquid of 40 ~ 60% being entered light constituent knockout tower is separated light constituent.
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| CN1530358A (en) * | 2003-01-24 | 2004-09-22 | 中国石油化工股份有限公司巴陵分公司 | Process for catalytic oxidation of cyclohexane |
| CN102260136A (en) * | 2010-05-26 | 2011-11-30 | 北京石油化工学院 | Method for preparing mixture of cyclohexanone and cyclohexanol by oxidazing cyclohexane liquid phase |
| CN102627541A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Technology for preparing hexanaphthene and cyclohexanone through cyclohexane oxidation and device thereof |
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| CN1530358A (en) * | 2003-01-24 | 2004-09-22 | 中国石油化工股份有限公司巴陵分公司 | Process for catalytic oxidation of cyclohexane |
| CN102260136A (en) * | 2010-05-26 | 2011-11-30 | 北京石油化工学院 | Method for preparing mixture of cyclohexanone and cyclohexanol by oxidazing cyclohexane liquid phase |
| CN102627541A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Technology for preparing hexanaphthene and cyclohexanone through cyclohexane oxidation and device thereof |
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