CN102675176A - Method for producing caprolactam by taking high-purity benzene as raw material - Google Patents
Method for producing caprolactam by taking high-purity benzene as raw material Download PDFInfo
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Abstract
The invention provides a method for producing caprolactam by taking high-purity benzene as a raw material, and the method comprises the following steps of: A. preparing cyclohexene from the raw material benzene through hydrogenation; B. separating and purifying cyclohexene; C. carrying out hydration on the cyclohexene for preparing cyclohexanol; D. separating and purifying cyclohexanol; E. carrying out dehydrogenation on cyclohexanol for preparaing cyclohexanone; F. refining cyclohexanone; G. carrying out oximation on cyclohexanone so as to prepare cyclohexanone-oxime; H. refining cyclohexanone-oxime; I. carrying out rearrangement on refined cyclohexanone-oxime so as to prepare caprolactam; and J. refining caprolactam, wherein the high-purity benzene is adopted as a raw material, so that the purity of benzene is more than 99.95%, the sulphur content is less than 5ppm, and the methylbenzene is not more than 100ppm. The method has the beneficial effects that the high-purity benzene is adopted as a raw material, so that the impurity is less, and the product quality is high; the raw material is high in comprehensive utilization rate and low in hydrogen consumption; and the mass of the raw material and intermediate products generated in all the steps of reaction can be strictly controlled, so that the direct commercial value of the intermediate products is fully exerted, and the optimal quality of the product caprolactam can be reached.
Description
Technical field
The invention belongs to technical field of chemical synthesis, relate to a kind of method of producing hexanolactam.
Background technology
Hexanolactam (CPL) is an important monomer of producing polyamide fibre 6 and nylon-6 engineering plastics, has excellent thermostability, processibility, mechanicalness and chemical-resistant.Be widely used in fields such as automobile, boats and ships, medical article, daily necessities, electronics and electronic component.
The method of producing hexanolactam in the industry mainly contains phynol method, toluene method and benzene method, because toluene and phenol price are higher, is not easy to obtain, and what account for main flow at present is the benzene method, accounts for 80% of world's total capacity.Traditional benzene method is produced hexanolactam and is comprised the prepared from benzene and hydrogen hexanaphthene, air oxidation of cyclohexane, decomposition preparing cyclohexanone, hydroxylammonium salt formulations prepared from solutions and pimelinketone oximate; OxiKhim-Styrol Beckmann rearrangement and neutralization and caprolactam refining; Ammonium sulfate extraction and recovery.
There is the low shortcoming of benzene utilization ratio in the above method; The raw material that causes in the various side reactions in air oxidation of cyclohexane unit only has the utilization ratio about 80%; Generate a large amount of unmanageable saponification waste-waters simultaneously; Adopt burning disposal not only to waste valuable resource, also need add postcombustion, increased energy expenditure.
Patent 96101020.7 discloses a kind of preparation method of hexanolactam, proposes the specification of quality that control is used to carry out the pimelinketone of oxyammonia oximate, but does not propose concrete control method; In addition, this technology adopts oxyammonia to carry out oximation reaction, long flow path; Investment is big, and by product is more.
It is the method for raw material production pimelinketone with the coking benzene that patent 200910075129.8 discloses a kind of, and its main innovate point is to adopt coking benzene as raw material, has proposed the production result under certain state parameter.But the quality control to raw material impurity requirement, intermediate product and the finished product in each step in the pimelinketone compound method does not propose concrete way.And this method only relates to the step by the coking benzene preparing cyclohexanone, do not explain whether the quality index of this pimelinketone can be used to produce hexanolactam, more do not relate to the production stage of hexanolactam.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art; Improve utilization ratio of raw materials; Reduction is to the pollution of environment, and for improving the quality of hexanolactam, selecting high pure benzene for use is the raw material production hexanolactam simultaneously; Middle quality product is carried out strictness control purify, and to have designed a cover be the compound method of raw material production hexanolactam with the high pure benzene for this reason.The objective of the invention is to realize like this:
A kind of is the method for raw material production hexanolactam with the high pure benzene, may further comprise the steps:
A benzene feedstock hydrogenation preparing tetrahydrobenzene; The B tetrahydrobenzene separates purifies; The C preparing cyclohexanol by cyclohexene hydration reaction; The D hexalin separates purifies; The E cyclohexanol dehydrogenation prepares pimelinketone; The F pimelinketone is refining; G pimelinketone oximate prepares OxiKhim-Styrol; The H OxiKhim-Styrol is refining; The I rearrangement of cyclohexanone-oxime prepares hexanolactam; The J caprolactam refining, what wherein benzene feedstock adopted is high pure benzene, and benzene purity is greater than 99.95%, and sulphur content is less than 5ppm, and toluene is not more than 100ppm.
Concrete steps are following:
1.1 pimelinketone preparation
A. the benzene partial hydrogenation prepares tetrahydrobenzene: high pure benzene and hydrogen are under the effect of hydrogenation catalyst, and 135～150 ℃ of temperature of reaction are reacted under reaction pressure 4.8～5.5MPaG.
B. tetrahydrobenzene separates: reaction solution through extracting rectifying accomplish dehydration, take off benzene, benzene reclaims, tetrahydrobenzene separates, tetrahydrobenzene is refining and process such as solvent treatment, finally can obtain the tetrahydrobenzene product of purity greater than 99.8%wt.Isolated hexanaphthene obtains purity greater than 99.9% hexanaphthene sub product through refining the purification.
C. cyclohexene hydration: tetrahydrobenzene in hydration reactor, under catalyst action, 110～130 ℃ of temperature of reaction, reaction pressure 0.5～0.8MPaG down with water reaction generation hexalin.
D. hexalin is refining: hydration reaction liquid is through hexalin separation, the refining hexalin that obtains of hexalin.
E. preparing cyclohexanone by cyclohexanol dehydrogenation: hexalin is in shell and tube reactor, and under the dehydrogenation catalyst effect, in 210～240 ℃ of temperature of reaction, reaction pressure 0.01～0.1MPaG generates pimelinketone and hydrogen down.Through gas-liquid separator dehydrogenation hydrogen is separated with reaction solution.
F. pimelinketone is refining: dehydrogenation reaction liquid through light constituent separate, pimelinketone separates and separates the pimelinketone purity that obtains with hexalin greater than 99.95%wt., light constituent content is less than 200ppm.
G. dehydrogenation hydrogen recovery: dehydrogenation hydrogen is delivered to hydrogen purification system by compressor and after absorption is purified, is returned benzene partial hydrogenation cyclohexene and use as raw hydrogen.
1.2 OxiKhim-Styrol preparation
A. cyclohexanone oxamidinating: with the trimethyl carbinol make solvent, HTS is a catalyzer, pimelinketone, ammonia and ydrogen peroxide 50 reaction generate OxiKhim-Styrol.
B. t-butanol solvent is separated: through rectifying the trimethyl carbinol is separated with OxiKhim-Styrol.
C. extracting and separating: with toluene is extraction agent, cyclohexanone oxime and waste water.
D. rectifying separation: OxiKhim-Styrol-toluene is isolated toluene, is obtained OxiKhim-Styrol through two stage rectification, and OxiKhim-Styrol purity is greater than 99.9%.
E. reaction end gas reclaims: the trimethyl carbinol and the ammonia of reaction end gas in cooling, condensing and recycling tail gas absorbs the ammonia in the tail gas through the tail gas recovery tower washing again.
F. waste water stripping: the waste water that reaction waste that the steam stripped extracting and separating goes out and rectifying separation go out, the waste water behind the stripping drain into WWT.
1.3 hexanolactam preparation
A. OxiKhim-Styrol gets into multistage rearrangement reactor reaction in proportion and generates hexanolactam under the oleum catalyst action.
B. rearrangement product neutralizes with ammoniacal liquor, and neutralized reaction product gets into standing demix in the separator, and upper organic phase gets into the hexanolactam extraction tower, extracts hexanolactam with extraction agent; The inorganic sulphur ammonium extraction tower that gets into mutually of lower floor is with the inorganic hexanolactam in mutually of extraction agent extraction.
C. the hexanolactam that extracts gets into stripping column again, water reextraction hexanolactam.
D. extraction agent gets into the distillation tower recycling use.
E. get into refined unit through the hexanolactam of stripping, hexanolactam is carried out refinement treatment.
F. refining back hexanolactam gets into evaporation element, adopts triple effect evaporation or mechanical vapour recompression (MVR) method, and caprolactam concentration is increased to 90%.
G. the hexanolactam after the evaporation further distills, and obtains the finished product hexanolactam.
Described a kind of be in the method for raw material production hexanolactam with the high pure benzene,
Among the step 1.1A, what benzene feedstock adopted is high pure benzene, and wherein benzene purity is greater than 99.95%, and sulphur content is less than 5ppm, and toluene is not more than 100ppm; 135～150 ℃ of temperature of reaction, reaction pressure 4.8～5.5MPaG.Raw hydrogen purity is greater than 99%vol., and sulphur content wherein is less than 50ppb.Adopt the influence of impurity that high pure benzene can avoid bringing in the benzene feedstock, be convenient to control the quality product of hexanolactam hexanolactam.
Among the step 1.1A, the benzene partial hydrogenation prepares in the reactive system of tetrahydrobenzene and is provided with flash tank, and its bottom is provided with the catalyst recovery pipeline and delivers to the catalyst recovery unit and reclaim.
Among the step 1.1B, comprise dehydration, take off benzene, benzene reclaims, tetrahydrobenzene separates, tetrahydrobenzene is refining and six towers of solvent treatment, the purity of the tetrahydrobenzene that obtains can reach 99.8%wt., contains quantity of solvent less than 0.005%wt., can be directly as merchandise sales.
Among the step 1.1C, adopt 1～3 stage reactor, be preferably 2 grades; With the molecular sieve is catalyzer, is preferably type ZSM 5 molecular sieve, and tetrahydrobenzene and pure water reaction generate hexalin.
Among the step 1.1D, comprise refining three towers of hexalin separation, decylization hexene and hexalin, the purity of the hexalin that obtains is greater than 99.5%wt., and light constituent content is less than 0.3%wt..
Among the step 1.1E, adopt tubular fixed-bed reactor, loading catalyst in the pipe, the outer heat conduction wet goods that feeds of pipe provides reaction institute heat requirement.Temperature of reaction is 210～240 ℃, and reaction pressure is 0.01～0.1MPaG.
Among the step 1.1F, comprise drying tower, light constituent knockout tower, pure tower and four towers of ketone tower, the pimelinketone purity that obtains is greater than 99.95%wt., and heptanone content is less than 200ppm.
Among the step 1.1G, employing be adsorption unit, the hydrogen reclamation rate reaches more than 80%.
Among the step 1.2A, 75～83 ℃ of temperature of reaction, reaction pressure 0.35～0.45MPaG add the trimethyl carbinol aqueous solution, ydrogen peroxide 50 and gas ammonia in the reaction solution; Ydrogen peroxide 50 in molar ratio wherein: pimelinketone=1.1～1.3:1 and ammonia: pimelinketone=1.2～1.4: 1.Reaction back liquid filters to isolate reaction clear liquid that does not contain catalyzer and the turbid liquid of reaction that contains catalyzer.React turbid liquid and shift out reaction heat, control reaction temperature, prevent to react overtemperature and generate by product through water cooler.
Among the step 1.2B, the flash separation of reaction clear liquid elder generation is to get into trimethyl carbinol rectifying tower respectively after gas phase, the liquid phase, and cat head obtains containing the OxiKhim-Styrol of the trimethyl carbinol less than 100ppm--the aqueous solution at the bottom of isolating trimethyl carbinol He Shui, tower.
Described in the step 1.2C, toluene and OxiKhim-Styrol-aqueous solution, cooling, two-stage extracting and separating obtain OxiKhim-Styrol-toluene solution, isolate reaction waste.
Described in the step 1.2D; OxiKhim-Styrol and toluene are performed such isolating: OxiKhim-Styrol-toluene solution gets into first rectifying tower; Cat head is isolated toluene; The tower still obtains containing toluene 20～40% toluene-oxime solution, and still liquid advances second rectifying tower to be separated once more, and the tower still obtains purity greater than 99.9% OxiKhim-Styrol.
Among the step 1.2E, reaction end gas gets into the trimethyl carbinol and the ammonia in exhaust emissions water cooler, the condensing and recycling tail gas, and non-condensable gas gets into the tail gas recovery tower washing and absorbs the ammonia in the tail gas; The cat head non-condensable gas is through decomposing or the burning disposal qualified discharge.
Among the step 1.2F, the waste water that reaction waste that water vaporization tower goes out with the steam stripped extracting and separating and rectifying separation go out, the toluene in the recovered overhead waste water, toluene level is not more than 1% in the waste water behind the stripping.
Among the step 1.3A, OxiKhim-Styrol is under the catalyst action at oleum, gets into the rearrangement reactor reaction in proportion and generates hexanolactam, preferentially selects the secondary rearrangement reactor for use.OxiKhim-Styrol gets into one-level rearrangement reaction groove and secondary rearrangement reaction groove respectively, and ratio is 4:1.Catalyst concn is 102% oleum, wherein contains free state SO
3Be 8%.The ratio of oleum and OxiKhim-Styrol is 1.2～1.5: 1.One-level rearrangement reaction temperature is 100～110 ℃, and secondary rearrangement reaction temperature is 100～130 ℃, and reaction pressure is a normal pressure.
Among the step 1.3B, said rearrangement product crude caprolactam and oleum and 20% ammoniacal liquor carry out neutralization reaction, and reaction product is crude caprolactam and ammonium sulfate solution, get into standing demix in crude caprolactam water solution-sulphur ammonium separator afterwards.The crude caprolactam water solution overflow that the upper strata obtains about 70wt% gets in the crude caprolactam dashpot, is sent to extracting system; About 39wt% ammonium sulfate solution that lower floor obtains is sent to sulphur ammonium extraction tower and reclaims hexanolactam wherein.
In sulphur ammonium extraction tower, with extraction agent hexanolactam is wherein extracted, the preferred benzene of extraction agent, but be not limited to benzene.Ammonium sulfate solution gets into from cat head, and benzene gets at the bottom of tower, and separates at the top of tower, and the benzene-caprolactam solution of generation flows into the hexanolactam extraction tower through overflow mutually.The benzene that contains trace in the ammonium sulfate solution that comes out at the bottom of the tower is pumped to the benzene that sulphur ammonium stripping tower is removed trace.45 ℃ of cat head service temperatures, working pressure 10kPaG.
The aqueous solution-sulphur ammonium separator upper strata obtains the crude caprolactam water solution pumping of about 70wt% toward hexanolactam extraction tower top.Underlying liquid at the bottom of the hexanolactam extraction Tata drains into the phlegma stripping tower.At the top of hexanolactam extraction tower, the benzene of rising extracts hexanolactam from the aqueous solution, and overflow to hexanolactam benzole soln pump groove is pumped into stripping column more then.45 ℃ of cat head service temperatures, working pressure 10kPaG.
Among the step 1.3C, benzene-caprolactam solution gets at the bottom of the reextraction Tata.Phlegma from evaporization process gets into from cat head, the hexanolactam in benzene-hexanolactam drop that extraction is risen.The aqueous caprolactam at stripping column top separates with benzene, and the caprolactam water solution at the bottom of the tower gets into benzene stripping tower cat head.96 ℃ of benzene stripping tower cat head service temperatures, working pressure is 10kPaG.
Among the step 1.3D,, need distill, adopt double-effect rectification extraction agent for fear of impurities accumulation.Extraction agent be pumped into to the distillation one Tata at the bottom of.Heating thermal source at the bottom of the tower is a LP steam, and the steam of cat head is as the thermal source of distillation two towers, and condensed extraction agent recycles.Distilling two column overhead steam recycles after the interchanger condensation.Distill 118 ℃ of column overhead service temperatures, working pressure is 0.2MPaG.Distill 80 ℃ of two column overhead service temperatures, working pressure is a normal pressure.
Among the step 1.3E, still contain micro-impurity through the hexanolactam after the extraction, need through refined unit Impurity removal this moment.Refined unit includes but not limited to IX and two steps of hydrogenation at least.Hexanolactam after the extraction carries out IX through exchange resin tower, is pumped into to hydrogenator afterwards.Hydrogenator is a staged reactor, preferred second reactor.Hexanolactam after the IX gets into the 1# hydrogenator and reacts, and reactant gets into the 2# hydrogenator through the overflow mode and further carries out hydrogenation reaction.The hydrogenation reaction temperature is 90 ℃, and reaction pressure is 0.7MPaG.Catalyzer is a metal catalyst, Raney's nickel for example, platinum etc.
Among the step 1.3F, the caprolactam water solution behind the hydrogenation concentrates in two steps, is concentrated to 99.9% from 30%.The first step concentrates, and caprolactam water solution is concentrated into 90% in the triple effect evaporation tower, in this triple effect evaporation tower; In order to reduce the consumption of steam; Upper level is evaporated the reboiler that the steam that is used for next stage, and in order to make reboiler obtain enough temperature difference, the method for decompression is step by step adopted in evaporation.One effect evaporator tower top pressure is 250～350kPa (A), and the concentration of the hexanolactam that comes out in the bottom is about 35～45%, is disposed to two and imitates reboilers.After further being concentrated into 52～60%, the water vapour that caprolactam solution comes out through an effect evaporator tower is disposed to the triple effect reboiler.Two effect evaporator tower top pressures are 130～240kPa (A).Caprolactam solution further is concentrated into 90% through the water vapour that two effect evaporator towers come out in the triple effect evaporation tower.Triple effect evaporation top of tower pressure is 110～15kPa (A).Spissated hexanolactam is pumped in the vapor-liquid separation still vaporizer, is heated to 126 ℃ of entering separating still vapor-liquid separation and obtains 99% caprolactam solution, and the hexanolactam of bottom flow to flash distillation in the hexanolactam flash drum, obtains 99.9% hexanolactam.
Among the step 1.3G; 99.9% hexanolactam is delivered to distillation process; In this course, high boiling impurity and minor amount of water all are removed, for high as far as possible reclaimed hexanolactam from the bottoms of main distillation column; This product distills through the multistage distillation tower once more, preferred two-step distillation.99.9% hexanolactam is with being pumped to the hexanolactam evaporator for distillation; 70% of charging enters in the hexanolactam fractionation by distillation device after under 127 ℃ condition, evaporating in the hexanolactam evaporator for distillation; Make that vapor-liquid separation, the pressure at separator top are 0.5kPa (A).The hexanolactam steam at top is delivered in the discharge pump groove after the hexanolactam distiller condenser is by hot water cooling and condensation.Hexanolactam fractionation by distillation device bottoms drains in the residue fractionation by distillation device vaporizer; 70% of charging enters in the residue fractionation by distillation device after under 127 ℃ condition, evaporating in the residue evaporator for distillation; Make that vapor-liquid separation, the pressure at separator top are 0.5kPa (A).
The present invention has following beneficial effect:
1) adopts high pure benzene, avoided the generation of interstitial impurity, help improving the quality of product hexanolactam.
2) adopt the tetrahydrobenzene method to produce hexanolactam, the benzene feedstock utilization ratio is high, and three waste discharge is few, the saponification waste-water incinerator need be set.
3) dehydrogenation hydrogen is through handling reuse, and hydrogen consumption is low, only is equivalent to 60% of traditional hexanaphthene method.
4) hexanolactam hydrofining adopts two-step approach, and hydrogenation is complete, helps improving the quality of products.
5) triple effect evaporation is adopted in the hexanolactam evaporation, has reduced energy expenditure.
6) in the process method of the present invention, the quality of the intermediate product of strict control raw material and each step reaction not only can be given full play to the direct commercial value of intermediate product, and makes the quality of product hexanolactam reach optimum.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but does not limit protection scope of the present invention.
Embodiment 1
Below in conjunction with accompanying drawing and specific embodiment the present invention is described in detail.But accompanying drawing and specific embodiment are not construed as limiting the invention.
A kind of is the method for raw material production hexanolactam with the high pure benzene; It is realized like this: flow is that the high pure benzene of 15t/h gets into the benzene hydrogenation device through the measure control flow; Feed hydrogen simultaneously, ruthenium-containing catalyst adds in the reactor drum in advance, 145 ℃ of temperature of reaction; React the generation tetrahydrobenzene under the pressure 5MPaG, the part side reaction takes place simultaneously generate hexanaphthene.
Hydrogenation reaction product is separated tetrahydrobenzene, hexanaphthene and benzene through the tetrahydrobenzene separating unit.The benzene Returning reactor continues to use; Hexanaphthene is through purifying as sub product, and next workshop section sent into by tetrahydrobenzene and water carries out hydration reaction.
Sieve catalyst is used in hydration, 128 ℃ of control reaction temperature, and pressure 0.7MPaG, the flow of gate ring hexene are 140t/h, the flow 7t/h of water.The per pass conversion 10% of tetrahydrobenzene.
Hydrated product is sent into the hexalin separating unit and is made with extra care, and at first carries out separating of tetrahydrobenzene and hexalin.Unreacted tetrahydrobenzene returns the hydration reaction unit, then hexalin made with extra care, and hexalin purity 99.8%, methylcyclopentanol content is 0.2%.
The laggard dehydrogenation reactor of hexalin process preheating, dehydrogenation reaction pressure 20KPa, 230 ℃ of temperature adopt the copper Si catalyst, the transformation efficiency 50～60% of gate ring hexanol.Pure alcohol/ketone mixtures is back to dehydrogenation unit through the refining weight component that removes with the hexalin separation after the dehydrogenation, and pimelinketone concentration after purifying is 99.98%.
Flow is that the pimelinketone of 13.8t/h is sent into the Ammoximation reaction device; 80 ℃ of temperature of reaction, reaction pressure 0.45MPaG; Wherein use the trimethyl carbinol to make solvent, HTS is catalyzer; Ammonia and ydrogen peroxide 50 are reinforced in molar ratio, and reaction generates OxiKhim-Styrol, makes the reaction solution that contains OxiKhim-Styrol, liquefied ammonia, water, the trimethyl carbinol, catalyzer.Reaction solution is isolated reaction clear liquid that does not contain catalyzer and the turbid liquid of reaction that contains catalyzer through strainer.React turbid liquid and shift out reaction heat through water cooler, the reaction clear liquid obtains containing the OxiKhim-Styrol aqueous solution of the trimethyl carbinol less than 100ppm at the bottom of flash distillation, rectifying tower are isolated trimethyl carbinol He Shui, tower.
With toluene as extraction agent and OxiKhim-Styrol aqueous solution, be cooled to 50 ℃, the two-stage extracting and separating obtains OxiKhim-Styrol-toluene solution, isolates reaction waste.OxiKhim-Styrol-toluene is isolated toluene, is obtained OxiKhim-Styrol through two stage rectification, and OxiKhim-Styrol purity is 99.93%.
Rearrangement reaction takes place and generates hexanolactam under the catalyst action of 102% oleum in OxiKhim-Styrol in rearrangement reactor.Rearrangement product neutralizes with ammoniacal liquor, and neutralized reaction product gets into standing demix in the separator, and upper organic phase gets into the hexanolactam extraction tower, extracts hexanolactam with extraction agent; The inorganic sulphur ammonium extraction tower that gets into mutually of lower floor is with the inorganic hexanolactam in mutually of benzene extraction.The hexanolactam that extracts gets into stripping column again, water reextraction hexanolactam.Benzene gets into the distillation tower recycling use.Hexanolactam through stripping gets into refined unit, and hexanolactam is carried out obtaining 30% hexanolactam after the refinement treatment, and it gets into evaporation element, and caprolactam concentration is increased to 90%.Hexanolactam after the evaporation further distills, and obtains 99.9% finished product hexanolactam 15t/h.
More than preferred embodiment of the present invention is specified, but said content is merely preferred embodiment of the present invention, can not be considered to be used to limit practical range of the present invention.All equalizations of doing according to application range of the present invention change and improve etc., all should still belong within the patent covering scope of the present invention.
Claims (9)
1. one kind is the method for raw material production hexanolactam with the high pure benzene, it is characterized in that: comprise following steps: A benzene feedstock hydrogenation preparing tetrahydrobenzene; The B tetrahydrobenzene separates purifies; The C preparing cyclohexanol by cyclohexene hydration reaction; The D hexalin separates purifies; The E cyclohexanol dehydrogenation prepares pimelinketone; The F pimelinketone is refining; G pimelinketone oximate prepares OxiKhim-Styrol; The H OxiKhim-Styrol is refining; The I rearrangement of cyclohexanone-oxime prepares hexanolactam; The J caprolactam refining, what wherein benzene feedstock adopted is high pure benzene, and benzene purity is greater than 99.95%, and sulphur content is less than 5ppm, and toluene is not more than 100ppm.
2. according to claim 1 a kind of be the method for raw material production hexanolactam with the high pure benzene, it is characterized in that: in the described steps A benzene feedstock hydrogenation preparing tetrahydrobenzene, raw hydrogen purity is greater than 99%vol., and sulphur content is less than 50ppb.
3. according to claim 1 a kind of be the method for raw material production hexanolactam with the high pure benzene; It is characterized in that: described step B tetrahydrobenzene separates in the purification; Comprise dehydration, take off benzene, benzene reclaims, tetrahydrobenzene separates, tetrahydrobenzene is refining and six towers of solvent treatment; The purity of the tetrahydrobenzene that obtains reaches 99.8%wt., contains quantity of solvent less than 0.005%wt..
4. according to claim 1 a kind of be the method for raw material production hexanolactam with the high pure benzene; It is characterized in that: described step e cyclohexanol dehydrogenation prepares in the pimelinketone, and dehydrogenation hydrogen is delivered to hydrogen purification system by compressor and after absorption is purified, returned steps A and use as raw hydrogen.
5. according to claim 1 a kind of be the method for raw material production hexanolactam with the high pure benzene; It is characterized in that: during described step F pimelinketone is refining, dehydrogenation reaction liquid through light constituent separate, pimelinketone separates and separates the pimelinketone purity that obtains with hexalin greater than 99.95%wt..
6. according to claim 1 a kind of be the method for raw material production hexanolactam with the high pure benzene, it is characterized in that: during described step H OxiKhim-Styrol was refining, OxiKhim-Styrol purity was greater than 99.9%.
7. according to claim 1 a kind of be the method for raw material production hexanolactam with the high pure benzene; It is characterized in that: in the described step J caprolactam refining; The step that comprises hexanolactam hydrofining, this step adopts two-step approach, carries out IX earlier; And then carrying out hydrogenation, hydrogenation catalyst adopts metal catalyst.
8. according to claim 1 a kind of be the method for raw material production hexanolactam with the high pure benzene; It is characterized in that: in the described step J caprolactam refining, comprise extraction agent is carried out the distillatory step, adopt double-effect rectification; Distill 118 ℃ of column overhead service temperatures; Working pressure is 0.2MPaG, distills 80 ℃ of two column overhead service temperatures, the working pressure normal pressure.
9. according to claim 1 a kind of be the method for raw material production hexanolactam with the high pure benzene, it is characterized in that: in the described step J caprolactam refining, triple effect evaporation or mechanical vapour recompression method are adopted in hexanolactam evaporation.
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| CN102875348A (en) * | 2012-09-29 | 2013-01-16 | 中国天辰工程有限公司 | High-yield production method of cyclohexanone |
| CN102989185A (en) * | 2012-11-26 | 2013-03-27 | 中国化学赛鼎宁波工程有限公司 | Production system of dehydrated caprolactam and method thereof |
| CN103086968A (en) * | 2013-02-22 | 2013-05-08 | 湖南百利工程科技股份有限公司 | Method for refining caprolactam through fixed-bed hydrogenation |
| CN103864689A (en) * | 2012-12-07 | 2014-06-18 | 帝斯曼知识产权资产管理有限公司 | Method for preparing caprolactam |
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| CN106397088A (en) * | 2016-09-13 | 2017-02-15 | 中国天辰工程有限公司 | High-efficiency refining method for making cyclohexanone and producing cyclohexane as by-product by cyclohexene method |
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| CN106588536A (en) * | 2016-12-06 | 2017-04-26 | 福建永荣科技有限公司 | Preparation method and preparation system of cyclohexanone |
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