CN107915612A - A kind of method for the MIBK that purification is prepared by industrial by-product waste liquid acetone - Google Patents
A kind of method for the MIBK that purification is prepared by industrial by-product waste liquid acetone Download PDFInfo
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- CN107915612A CN107915612A CN201610875280.XA CN201610875280A CN107915612A CN 107915612 A CN107915612 A CN 107915612A CN 201610875280 A CN201610875280 A CN 201610875280A CN 107915612 A CN107915612 A CN 107915612A
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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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/73—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with hydrogenation
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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
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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
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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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
- C07C45/83—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by extractive distillation
Abstract
The invention discloses a kind of technical process that high-purity MIBK is prepared using industrial by-product waste liquid acetone.Reaction solution including synthesizing MIBK by waste liquid acetone obtains the light component than acetone low boiling point in cut light tower tower top, and unreacted acetone is obtained in acetone recycling column overhead；Boiling point is obtained less than the organic matter of MIBK/ water azeotropic mixtures and the azeotropic mixture of MIBK/ water in process water column overhead；The low-boiling-point organic compounds such as the acetone from raw material, methanol are obtained in dehydration column overhead；Alcohol/water distillate is obtained in dealcoholysis column overhead and obtains thick MIBK distillates in tower reactor；MIBK refine column overhead obtain boiling point less than MIBK light component and side line obtain the MIBK products of purity >=99.5%.Techniqueflow disclosed by the invention is succinct, energy consumption is low, production cost is low, and the MIBK products of high-purity are obtained using high impurity waste liquid acetone, possess significant economic benefit.
Description
Technical field
The present invention relates to a kind of production method of the MIBK of purification, and specifically one kind is by industrial by-product waste liquid acetone
The method for producing the MIBK of purification.
Technical background
Conjugated oxidation propylene oxide process is the prevailing technology of industrial production propylene oxide, including PO/TBA techniques and
PO/SM techniques, about 10,000,000 tons/year of current whole world PO device capbilities, wherein conjugated oxidation technique accounts for 55%~60%.Because
The oxidation reaction of conjugated oxidation is radical reaction, and intermediate product activity is high, product is complex.Industrial conjugated oxidation epoxy
The a large amount of waste liquids of propane device by-product, this strand of waste liquid composition is complicated, and major impurity is epoxy iso-butane, first in addition to containing a large amount of acetone
Alcohol, tert-butyl alcohol etc., since boiling point difference is small between component, and there are methanol/acetone, acetone/epoxy iso-butane, butanol/water etc.
Multigroup azeotropic, conventional separation are unable to reach satisfied separating effect.Therefore, the utilization of this strand of material is severely limited, industry
On be commonly used as organic waste materials and burn recovery section heat, utility value is extremely limited.
CN201410128345 discloses a kind of method that MIBK is prepared using waste liquid acetone, by using advanced catalysis
And hydrogen addition technology, acetone is realized to the Efficient Conversion of MIBK, while is cleverly avoided component boiling point and approached, exist again
Miscellaneous azeotropism etc. is influenced caused by feedstock purification.
Methyl iso-butyl ketone (MIBK) (MIBK) is a kind of medium-boiling solvent of high comprehensive performance, while is also a kind of widely used
Acetone downstream derivative product, be mainly used in the industrial solvent such as coating, paint, lubricating oil dewaxing field, and synthetic rubber
The important source material of antioxidant and other chemical products.The mainstream preparation process of industrial MIBK is acetone through one-step method at present, raw material
Acetone specification is generally 99.5% industrial primes.
In method disclosed in CN201410128345, using the by-product waste liquid acetone conduct of conjugated oxidation propylene oxide unit
Raw material one-step synthesis method MIBK, avoids the complicated purification problem of raw material, realizes the efficient utilization of acetone, economic benefit is shown
Write.But product composition is more complicated at the same time, and separating difficulty increased compared with traditional handicraft.
The purifying technique for MIBK is the MIBK products prepared for pure acetone one-step method at present, and for industrial secondary
The waste liquid acetone of production prepare the purification of MIBK there is no literature reported on, it is therefore desirable to seek a kind of to be produced by industrial by-product waste liquid acetone
The new method of the MIBK of purification.
The content of the invention
It is an object of the invention to provide it is a kind of by industrial by-product waste liquid acetone production purification MIBK method, solve because
Use the separation that waste liquid acetone brings for raw material introducing plurality of impurities difficult, there is provided the separation method and technique mistake of a kind of optimization
Journey, to simplify product manufacturing process, reduces cost, obtains high-purity MIBK products.
To reach above goal of the invention, technical scheme is as follows：
A kind of method for the MIBK that purification is prepared by industrial by-product waste liquid acetone, comprises the following steps：
(i) in conversion zone, by industrial by-product waste liquid acetone through being condensed, being dehydrated and hydrogenation catalyst reaction generation MIBK and reality
Largely conversion obtains MIBK Synthesis liquids to existing impurity；
(ii) enter cut light tower after MIBK Synthesis liquids separation hydrogen and carry out extracting rectifying, removed overhead light component, tower
Kettle liquid phase stream enters acetone recovery tower；
(iii) the tower reactor liquid phase stream of (ii) step is through acetone recovery tower extracting rectifying, in the unreacted acetone of recovered overhead,
Tower reactor liquid phase stream obtains the logistics of rich aqueous phase and the logistics rich in organic phase after phase separation；
(iv) logistics of rich aqueous phase enters technique water tower, and tower top obtains the organic matter that boiling point is less than MIBK/ water azeotropic mixtures
And the azeotropic mixture of MIBK/ water enters dehydrating tower, tower bottoms part enters cut light tower, or cut light tower and acetone recycling
Tower；
(v) rich in organic phase logistics and process water column overhead stream (boiling point less than MIBK/ water azeotropic mixtures organic matter and
The azeotropic mixture of MIBK/ water) enter dehydrating tower, dehydrating tower is dividing wall column, and process water column overhead stream enters from dehydrating tower side,
Logistics rich in organic phase enters from the public rectifying section of dehydrating tower, and liquid-liquid quantizer, side are set on dehydrating tower opposite side column plate
Line obtains the distillate of the water/alcohol for being substantially free of MIBK (MIBK contents are less than 10wt%) close to azeotropic water/alcohol composition composition,
Removed overhead acetone, methanol, tower reactor obtain being substantially free of the liquid phase stream of water (water content is less than 0.2wt%)；
(vi) dehydrating tower tower reactor liquid phase stream enters dealcoholysis tower, and in removed overhead impurity alcohols, tower reactor obtains thick MIBK
Distillate enters MIBK treating columns, removed overhead light component, side take-off MIBK products after refining.
As a kind of preferable concrete scheme, the method bag of the MIBK that purification is prepared by industrial by-product waste liquid acetone
Include following steps：
(i) in conversion zone, by industrial by-product waste liquid acetone through being condensed, being dehydrated and hydrogenation catalyst reaction generation MIBK and reality
Largely conversion obtains MIBK Synthesis liquids to existing impurity；
(ii) cut light tower is entered after MIBK Synthesis liquids separation hydrogen, hydrogen is recycled into conversion zone, described
Contain MIBK, acetone, water, isopropanol, diacetone alcohol, DIBK (diisobutyl ketone), iso-butane, 2- methylpents in MIBK Synthesis liquids
Alkane, methanol, the tert-butyl alcohol, isobutylaldehyde, isobutanol and methyl ethyl ketone (MEK) from raw material, ethers；
(iii) the MIBK Synthesis liquids after hydrogen are separated extracting rectifying is carried out in the presence of extractant through cut light tower, will
Light component containing iso-butane, 2- methylpentanes, isobutylaldehyde, methyl ethyl ketone and ethers enters tower reactor from removed overhead, heavy constituent,
Obtained tower reactor liquid phase stream enters acetone recovery tower；
(iv) the tower reactor liquid phase stream of (iii) step carries out extracting rectifying through acetone recovery tower in the presence of extractant, in tower
Unreacted acetone is recycled on top, and heavy constituent enters acetone recovery tower tower reactor, and obtained tower reactor liquid phase stream enters water knockout drum；
(v) the tower reactor liquid phase stream of (iv) step is separated into the thing of logistics and rich aqueous phase rich in organic phase through water knockout drum
Stream；
(vi) logistics of (v) step richness aqueous phase enters the organic matter in the logistics of the rich aqueous phase of technique water tower recycling, at the same time
Realize the recycling of extractant, tower top obtain boiling point less than the organic matter of MIBK/ water azeotropic mixtures and the azeotropic mixture of MIBK/ water into
Enter dehydrating tower, the tower bottoms of 60wt%~98wt% enters cut light tower, the tower bottoms of 0wt%~20wt% as extractant
Enter acetone recovery tower as extractant, remaining is discharged as waste water；The boiling point is less than the organic matter of MIBK/ water azeotropic mixtures
Azeotropic mixture including acetone, methanol, isopropanol, the tert-butyl alcohol, MIBK and water etc.；
(vii) separated logistics and the separated boiling point of technique water tower rich in organic phase are total to less than MIBK/ water in water knockout drum
The azeotropic mixture of the organic matter and MIBK/ water that boil thing enters dehydrating tower, and dehydrating tower is dividing wall column, the separated low boiling point of technique water tower
Enter in the organic matter of MIBK/ water azeotropic mixtures and the azeotropic mixture of MIBK/ water from dehydrating tower side, there is separated be rich in water knockout drum
The logistics of machine phase enters from the public stripping section of dehydrating tower, and liquid-liquid quantizer, liquid-liquid are set on dividing wall column opposite side column plate
Filler is housed, side line obtains the distillate of water/alcohol of the MIBK contents less than 10wt%, removed overhead acetone, first inside quantizer
Alcohol etc., tower reactor obtain the liquid phase stream that water content is less than 0.2wt%；
(viii) dehydrating tower tower reactor liquid phase stream enters dealcoholysis tower, and in removed overhead impurity alcohols, tower reactor obtains thick
MIBK distillates enter MIBK treating columns；The wherein described impurity alcohols includes isopropanol, the tert-butyl alcohol, isobutanol etc.；
(ix) MIBK treating columns removed overhead light component, part heavy constituent such as diacetone alcohol (DAA) etc. can decompose,
Distillation stage obtains the light components such as DAA catabolite acetone, side take-off MIBK products, and tower reactor obtains the high-boiling components thing containing DIBK
Stream.
In the present invention, the industrial by-product acetone comes from propylene oxide/tert-butyl alcohol combined production device, more specifically from altogether
Oxidizing process propylene oxide/tert-butyl alcohol device, based on waste liquid acetone weight, it includes water 0.1wt%~5wt%, methanol 0.5wt%
~6wt%, epoxy iso-butane 1wt%~20wt%, acetone 60wt%~95wt%, isopropanol 0.01wt%~0.5wt%, first
Ethyl ketone 0.01wt%~0.2wt%, tert-butyl alcohol 1wt%~15wt%, aldehydes (isobutylaldehyde etc.) 0.01wt%~2wt%, ethers
(methyl tertiary butyl ether(MTBE), isopropyl tertbutyl ether, n-propyl tertbutyl ether, isobutyl group tertbutyl ether etc.) 0.01wt%~5wt%.
Can be catalyzed condensation of acetone, dehydration, hydrogenation for the catalyst of the conversion zone of step (i) in the present invention
Prepare any solid catalyst of MIBK.Hydrogenation reaction in gas phase can also carry out in liquid phase, preferably in liquid phase bar
Carried out under part.The catalyst includes but not limited to Pd- resin compoundeds catalyst, Pd-ZSM-5 composite catalysts, Pd/Al2O3Urge
Agent or Ni/Al2O3Catalyst.It is preferred that the catalyst such as Pd- ion exchange resin composite catalyst under liquid-phase condition is used, this
The typical case of kind liquid-phase condition is, including uses about 80~160 DEG C of temperature and the pressure of 25Bar~75Bar, preferably
Pressure in the range of 25Bar~45Bar.
The crude reaction product separated from conversion zone, containing the MIBK as product, not reacted acetone, reaction production
Raw water impurity, isopropanol, diacetone alcohol, DIBK, 2- methylpentane, and brought into as impurity from waste liquid acetone raw material
React including impurity in methanol, the tert-butyl alcohol, methyl ethyl ketone, ethers etc. and raw material by conversion zone under catalyst action generation
Iso-butane, isobutylaldehyde etc..In fact, the acetone of 45~75wt% is included in MIBK Synthesis liquids, and the MIBK of 18~35wt%, 4
The water of~10wt%, the isopropanol of 0.01~2wt%, the diacetone alcohol of 0~1wt%, the DIBK of 0.1~2wt%, 0.01~
2wt% iso-butanes, the 2- methylpentanes of 0.001~0.5wt%, the methanol of 0.01~6wt%, the tert-butyl alcohol of 0~8wt%, 0.1
The isobutylaldehyde of~15wt%, the isobutanol of 0.01~15wt%, and the methyl ethyl ketone from 0.01~0.2wt% of raw material and 0.01
The ethers of~5wt%.
Using traditional fractional method, it is impossible to satisfactorily separated such a mixture, because such a mixture
In there are various ingredients to form binary or polynary azeotropic mixture between each other.Meanwhile the azeotropic mixture composition of the system is most
It is unrelated with pressure, or cannot to find suitable pressure range all effective to all azeotropic mixtures, it is thus impossible to logical
Cross and change pressure to realize the separation of above-mentioned azeotropic mixture.But by dehydrogenation component tower and acetone recovery tower using extraction
In the separation process that agent carries out extracting rectifying and carry out for light component and unreacted raw material acetone, it can be made
The fractionating effect of people's satisfaction.When cut light tower Solvent quantity is larger, the ratio of acetone recovery tower extractant can be reduced suitably
Even it is not added with extractant.
In the present invention, the cut light tower is extractive distillation column, extractant and carrys out the reaction solution of autoreactor at the same time
Add in tower.One or more mixtures of the extractant in monoethanolamine, ethylene glycol, hexylene glycol and water, preferably water are made
For extractant.Cut light tower operates under conditions of 80~300KPaA of pressure, preferably 100~200KPaA；Theoretical cam curve
For 15~60, preferably 25~50；Feed entrance point is the 10th~30 block of plate, preferably the 15th~25 block of plate；Reflux ratio is 2~50, excellent
Select 5~25.The coal addition position of extractant is identical with feeding liquid coal addition position or higher than feeding liquid coal addition position, preferably the 2nd~20
Block theoretical plate (is counted, similarly hereinafter) from top to bottom.The ratio of extractant and feeding liquid is 0.05~5:1, preferably 0.1~3:1.Especially
It is that when the extractant of light component, can allow containing light components such as 2- methylpentanes using water as 2- methylpentanes
With the mixture of acetone, it is separated into one and contains the light components such as 2- methylpentanes and acetone ratio and be less than 30wt%, preferably smaller than
The logistics of 10wt%, more preferably less than 5wt%, and one contains acetone and wherein 2- methylpentanes equal size is less than
The logistics of 0.02wt%, preferably smaller than 0.01wt%, more preferably less than 50PPm.
In the present invention, acetone recovery tower operates under conditions of pressure is 50~100KPaA, in order that preferably taking into account phase
To volatility and cooling-water consumption；Acetone recovery tower is extractive distillation column, extractant may be selected monoethanolamine, ethylene glycol, oneself two
One or more mixtures in alcohol and water, preferably water is as extractant.The mass ratio of Solvent quantity and feeding liquid for 0~
5:1, preferably 0~3:1.Tower top temperature is 40~60 DEG C, and bottom temperature is 70~90 DEG C；Theoretical cam curve is 10~100, preferably
30~60；Feed entrance point is the 5th~60 block of plate, preferably the 15th~40 block of plate；Reflux ratio is 0.5~5, preferably 0.5~3；Extraction
The coal addition position of agent is identical with feeding liquid coal addition position or higher than feeding liquid coal addition position, preferably the 2nd~20 piece of theoretical plate.Acetone
Recycling column overhead acetone purity can purify to 85%~99%, and tower reactor content of acetone is less than 1wt%, preferably shorter than 0.5wt%, more
Add preferably shorter than 0.2wt%.
In the present invention, acetone recovery tower tower bottoms is separated into the thing of logistics and rich aqueous phase rich in organic phase by water knockout drum
Stream.The logistics of wherein rich aqueous phase enters the recycling of technique water tower and is dissolved in MIBK therein and the organic matter lighter than MIBK,
The recycling of extractant water is realized at the same time.Logistics and process water column overhead stream rich in organic phase respectively enter dehydration
Tower.
In the present invention, technique water tower is 50~200KPaA in pressure, is operated under conditions of preferably 80~160KPaA；It is theoretical
The number of plates 5~30, preferably 10~25；Feed entrance point is 2~20 blocks of plates, preferably the 2nd~15 block of plate；Reflux ratio is 0.1~10,
It is preferred that 1~5.
In the present invention, dehydrating tower is side take-off tower, and is equipped with liquid-liquid quantizer in tower, is obtained by side take-off
The distillate of water/alcohol of the MIBK contents less than 10wt%.Due to containing from water knockout drum in the separated logistics rich in organic phase
More alcohol such as isopropanol, isobutanol, tert-butyl alcohol etc., can influence the layered effect of side take-off, and dehydrating tower is arranged to partition wall
Tower, the logistics rich in organic phase are fed from the side of dehydrating tower, and liquid-liquid quantizer is arranged on the opposite side of dehydrating tower, Neng Gouyou
The layered effect promoted on column plate of effect, while reduce the loss amount of MIBK.
In the present invention, dehydrating tower operates under conditions of 50~500KPaA of pressure, preferably 100~260KPaA；Reflux ratio
For 1~30, preferably 5~15；Theoretical cam curve is 20~80 pieces, preferably 20~60 pieces.The dehydrating tower top is public essence
Section is evaporated, lower part is public stripping section, and side is the next door tower section of charging, and opposite side is the next door tower section of side take-off, wherein into
The next door tower section of material is divided into boiling point less than top at the organic matter of MIBK/ water azeotropic mixtures and MIBK/ water azeotropic mixture chargings and public affairs again
Tower section at tower section and charging between common rectifying section lower end between lower section and public stripping section upper end.The next door tower of side take-off
Section is divided into lower section and public stripping section at the tower section at side take-off between top and public rectifying section lower end and side take-off again
Tower section between upper end.
Preferably, the theoretical cam curve of public rectifying section account for dehydrating tower theoretical tray sum 5~50%, preferably 10~
30%；Boiling point less than MIBK/ water azeotropic mixtures organic matter and MIBK/ water azeotropic mixture chargings at top with public rectifying section lower end it
Between theoretical cam curve account for dehydrating tower theoretical tray sum 5~30%, preferably 10~25%；Boiling point is less than MIBK/ water azeotropic
Theoretical cam curve at the organic matter of thing and MIBK/ water azeotropic mixture chargings between lower section and public stripping section upper end accounts for dehydrating tower reason
By 10~50%, preferably the 10~35 of column plate sum；Theoretical tray at side take-off between top and public rectifying section upper end
Number accounts for 10~50%, preferably the 10~35% of dehydrating tower theoretical tray sum；Lower section and public stripping section upper end at side take-off
Between theoretical cam curve account for dehydrating tower theoretical tray sum 5~30%, preferably 10~25%；The theoretical tower of public stripping section
Plate number accounts for 5~50%, preferably the 20~40% of dehydrating tower theoretical tray sum.Logistics rich in organic phase is in the public of dehydrating tower
Stripping section feeding, any one block of theoretical tray of the optional public stripping section of feed entrance point.
In the present invention, the filler of filling includes filler A and B in liquid-liquid quantizer on the column plate of dehydrating tower side.Wherein filler
A is modified super hydrophilic metal packing, and filler B is modified super oleophylic metal packing, and filler A is seated in lower floor, filler B
Upper strata is seated in, filler A and filler B fillings height are than being 1:8~4:1, preferably 1:4~2:1.
In the present invention, the filler A is that metal packing (such as stainless steel, carbon steel) is put into the solution of strong oxidizing property
12~18h of processing is carried out, is obtained afterwards with deionized water rinsing to neutrality, the preferred potassium bichromate of solution of the strong oxidizing property
Sulfuric acid and/or potassium permanganate sulfuric acid solution.In filler A surface sprayings upper surface modifying agent and auxiliary agent, add at 200~300 DEG C
Hot 30min~60min, you can filler B is obtained, wherein, surface modifier preferably polytetrafluoroethylene lotion, the preferred sulfonation of auxiliary agent gathers
The mass ratio of acid imide lotion, wherein ptfe emulsion and sulfonated polyimide lotion addition is 1:1~20:1, preferably 5:
1~10:1, the quality summation of surface modifier and auxiliary agent accounts for the 0.001%~1% of filler A mass, preferably 0.01~0.1%.
By carrying out oxidation processes to metal packing surface, the degree of roughness on filler surface is improved, enhances filler pair
The wetability of water, by it is filler modified be super hydrophilic filler.The surface modifier of filler B surface can be inhaled on the coarse surface of filler
It is attached, microscopic, spherical or bulk can be formed in the groove on filler surface after dry, plays the super-hydrophobic effect of super oleophylic.Dividing
The upper lower leaf of filler A and filler B loads in layer device, not only preferably promotes the separation of water-oil phase, but also improve tower
The ability of mass-and heat-transfer on plate.The addition of auxiliary agent in filler B, makes to introduce sulfonic group on filler, and sulfonic introducing makes to be dissolved in
On filler surface dehydration occurs for the tert-butyl alcohol in oil phase, generates isobutene and water, the water of generation depart from super oleophylic and surpasses quickly
Hydrophobic filler enters water phase, and isobutene is gas, is discharged from tower top, since reaction is reversible reaction, promotes reaction to just
The direction of reaction is developed.Meanwhile the conversion of the tert-butyl alcohol also promotes the layering of water-oil phase in oil phase.
In the present invention, isopropanol, a small amount of tert-butyl alcohol, azeotropic mixture and the other alcohol lighter than MIBK of MIBK and isobutanol alcohol
Class component is removed from dealcoholysis column overhead.Dealcoholysis tower operates under conditions of 80~300KPaA of pressure, preferably 100~200KPaA；
Theoretical cam curve is 15~55, preferably 20~40 blocks of plates；Feed entrance point is the 5th~35 block of plate, preferably the 15th~25 block of plate；Reflux
Than for 5~50, preferably 5~30.
In the present invention, MIBK treating columns are 50~300KPaA in pressure, are operated under conditions of preferably 100~200KPaA；
Theoretical cam curve 20~60, preferably 30~50；Feed entrance point is the 10th~40 block of plate, preferably the 15th~20 block of plate；Reflux ratio is
20~150, preferably 50~120.
The separation method disclosed by the invention that high-purity MIBK is prepared using industrial wastes acetone, is solved because raw material introducing is miscellaneous
Separation is difficult caused by matter, while is in view of the problems of the existing technology improved.Pass through extracting rectifying, dividing wall column
Technology greatly reduces the loss of acetone and MIBK products, and flow is more succinct, and investment reduces, energy consumption is saved, and can obtain
The product of high-purity is obtained, possesses significant technology and economic sexual clorminance.The efficient utilization of final achievable waste liquid acetone, economy effect
It is beneficial notable.
Heretofore described pressure is absolute pressure.
Brief description of the drawings：Fig. 1 is the process flow chart of the MIBK that purification is prepared by industrial by-product waste liquid acetone of the present invention.
Embodiment：
For the clearer technique explained disclosed in the present invention, and readily implement and operate to utilize conjugated oxidation epoxy
Propane device by-product waste liquid acetone produces the selection process process and device of high-purity MIBK, below to the technical process of the present invention into
Row further description.
Personnel in the art will recognize that, due to attached drawing be it is schematical, on a set of commercial plant
Also need to some other equipment, such as condenser, heat exchanger, return tank, tower reboiler, pump, vacuum pump, temperature sensor, pressure
Force snesor, relief valve, control valve, flow controller, liquid-level controller, receiving tank, storage tank etc..On these ancillary equipments
Specification requirement is not belonging to the discussion scope of the present invention, can be accounted for according to conventional Chemical Engineering Technology.
The present invention is further discussed below with reference to the accompanying drawings：
As shown in Figure 1, wherein C-100 is cut light tower, C-101 is acetone recovery tower, and C-102 is dehydrating tower, C-103
For dealcoholysis tower, C-104 is MIBK treating columns, and C-105 is technique water tower.(main component has acetone, first to waste liquid acetone (stream stock 1)
Alcohol, water, epoxy iso-butane, isopropanol, methyl ethyl ketone, the tert-butyl alcohol, aldehydes, ethers etc.) and from acetone recovery tower C-101 recycling third
Ketone (stream stock 9) mixing enters reactor R-100 together with hydrogen (stream stock 2), and condensation dehydration hydrogenation occurs in reactor R-100
Reaction, generate material and unreacted hydrogen (stream stock 3) through hydrogen gas segregator D-100 by unreacted hydrogen (stream stock 4) and
MIBK Synthesis liquids (stream stock 5) separation.MIBK Synthesis liquids (main component MIBK, acetone, water, isopropanol, diacetone alcohol, DIBK,
Iso-butane, 2- methylpentanes, methanol, the tert-butyl alcohol, isobutylaldehyde, isobutanol and methyl ethyl ketone from raw material, ethers etc.) first into
Enter cut light tower C-100.Cut light tower is extraction tower, and extractant 6 enters from the position of the charging above, cut light tower
Main function is the light component sloughed in Synthesis liquid, including the light component such as 2- methylpentanes, iso-butane, ethers, and stream stock 7 is from tower top
Extraction, tower bottoms (stream stock 8) enter acetone recovery tower C-101.The main function of acetone recovery tower is the unreacted acetone of recycling,
Separation through acetone recovery tower, tower top obtain acetone (stream stock 9) of the purity much larger than raw material (stream stock 1) purity, tower bottoms (stream stock
10) water knockout drum D-101 is entered.In water knockout drum D-101, water-oil phase, oil phase (stream stock 11) are divided into based on alternate liquid-liquid equilibrium
Into dehydrating tower C-102, water phase (stream stock 12) enters technique water tower.Process water column overhead (stream stock 13) recycling boiling point is less than
The organic matter of MIBK/ water azeotropic mixtures enters dehydrating tower, and tower bottoms (stream stock 14) is recycled in the form of extractant, only
A small amount of water discharge (stream stock 15).Tower top (stream stock 16) abjection acetone, methanol, isobutene of dehydrating tower C-102 etc., side take-off
(stream stock 17) water and a small amount of alcohols, tower bottoms (stream stock 18) enter dealcoholysis tower C-103.In dealcoholysis column overhead removing isopropanol etc.
Alcohols (stream stock 19), tower bottoms (stream stock 20) enter MIBK treating columns C-104.Column overhead, which is refined, in MIBK obtains DAA decomposition productions
The light components such as raw a small amount of acetone (stream stock 21), MIBK product (stream stock 22) of the side take-off purity more than 99.5%, tower bottoms
(stream stock 23) is heavy constituent.
Comparative example
By waste liquid acetone mixture, atmospheric distillation separates in the rectifying column of Ф 26mm, and filler uses the triangle spiral shell of Ф 3*3
Rotation, pillar height 1.5m, overhead condensation coolant-temperature gage are 25 DEG C, 52-57 DEG C of overhead extraction temperature, reflux ratio 10:1, overhead extraction sample
Composition it is as shown in table 1.
Acetone is recycled in 1 by-product acetone mixture rectifying of table
As seen from the above table：Under broad theory plate number, big reflux ratio during rectification and purification acetone, methanol, epoxy iso-butane, third
Ketone, isopropanol, methyl ethyl ketone, aldehydes and ethers are almost without separation.It is difficult thus directly to recycle acetone in mixed liquor, it is necessary to
Design other acetone application approaches.
The composition of raw materials used waste liquid acetone is as shown in table 2 in each embodiment：
The composition of 2 raw material waste liquid acetone of table
Reactor R-100 conditions are as shown in table 3 in each embodiment：
Reactor condition in 3 each embodiment of table
| Reaction condition | Embodiment one | Embodiment two | Embodiment three |
| Reaction temperature DEG C | 80 | 100 | 160 |
| Reaction pressure/bar | 45 | 30 | 25 |
| Catalyst | Pd- resin catalysts | Pd- resin catalysts | Pd-Al2O3 |
Pd- resin catalysts：DOW Chemical Co., Ltd, wherein Amberlyst CH-28, Pd contents are 0.7wt%.
Embodiment 1
As shown in the flow of attached drawing, press table 4 after Synthesis liquid dehydrogenation will be reacted and the rectifying condition of table 5 carries out rectifying, wherein
The extractant of cut light tower is water, and the mass ratio of dosage and feeding liquid is 3:1, added in the 2nd piece of theoretical plate, wherein dehydrating tower
The height ratio of filler A and filler B on the column plate of side in liquid-liquid quantizer are 1:4, obtain that the results are shown in Table 6.From table 6
Understand：By the rectifying of each rectifying column, the mass fraction for finally obtaining MIBK products is 99.56%.
The preparation method of filler A and filler B are as follows：Stainless steel helices is put into potassium permanganate sulfuric acid solution and is handled
18h, obtains filler A with deionized water rinsing to neutrality afterwards.Ptfe emulsion and sulfonation gather on filler A surface sprayings
Acid imide lotion, heating 30min obtains filler B, the wherein matter of ptfe emulsion and sulfonated polyimide lotion at 250 DEG C
Amount is than being 5:1, the quality summation of surface modifier and auxiliary agent accounts for the 0.02% of filler A mass.
The rectifying condition of 4 rectifying column of table
| Rectifying column | C-100 | C-101 | C-103 | C-104 | C-105 |
| Number of theoretical plate | 15 | 50 | 30 | 60 | 30 |
| Feed entrance point | 10 | 30 | 15 | 40 | 20 |
| Pressure/KPaA | 100 | 100 | 300 | 50 | 50 |
| Reflux ratio | 50 | 0.5 | 5 | 100 | 4 |
The rectifying condition of 5 dehydrating tower C-102 of table
6 rectifying result of table
Embodiment 2
As shown in the flow of attached drawing, press table 7 after Synthesis liquid dehydrogenation will be reacted and the rectifying condition of table 8 carries out rectifying, wherein
The extractant of cut light tower is water, and the mass ratio of dosage and feeding liquid is 2:1, added in the 5th piece of theoretical plate, wherein dehydrating tower
The height ratio of filler A and filler B on the column plate of side in liquid-liquid quantizer are 1:1, obtain that the results are shown in Table 9.From table 9
Understand：By the rectifying of each rectifying column, the mass fraction for finally obtaining MIBK products is 99.67%.The system of filler A and filler B
Preparation Method is as shown in embodiment one.
The rectifying condition of 7 rectifying column of table
| Rectifying column | C-100 | C-101 | C-103 | C-104 | C-105 |
| Number of theoretical plate | 30 | 100 | 55 | 20 | 5 |
| Feed entrance point | 20 | 40 | 35 | 10 | 2 |
| Pressure/KPaA | 300 | 50 | 80 | 200 | 100 |
| Reflux ratio | 2 | 2 | 30 | 150 | 10 |
The rectifying condition of 8 dehydrating tower C-102 of table
9 rectifying result of table
Embodiment 3
As shown in the flow of attached drawing, press table 10 after Synthesis liquid dehydrogenation will be reacted and the rectifying condition of table 11 carries out rectifying, its
The extractant of middle cut light tower is water, and the mass ratio of dosage and feeding liquid is 0.1, is added in the 20th piece of theoretical plate, acetone returns
The extractant for receiving tower be water, and the mass ratio of dosage and feeding liquid is 0.3, in the 2nd piece of theoretical plate addition, wherein dehydrating tower side tower
The height ratio of filler A and filler B on plate in liquid-liquid quantizer are 1:4, it is as shown in table 12 to obtain result.As can be known from Table 12：
By the rectifying of each rectifying column, the mass fraction for finally obtaining MIBK products is 99.72%.
The rectifying condition of 10 rectifying column of table
| Rectifying column | C-100 | C-101 | C-103 | C-104 | C-105 |
| Number of theoretical plate | 60 | 10 | 15 | 40 | 15 |
| Feed entrance point | 30 | 5 | 5 | 20 | 10 |
| Pressure/KPaA | 80 | 70 | 140 | 300 | 200 |
| Reflux ratio | 20 | 5 | 50 | 20 | 0.1 |
The rectifying condition of 11 dehydrating tower C-102 of table
12 rectifying result of table
Claims (12)
1. a kind of method for the MIBK that purification is prepared by industrial by-product waste liquid acetone, comprises the following steps：
(i) in conversion zone, by industrial by-product waste liquid acetone through being condensed, being dehydrated and hydrogenation catalyst reaction generation and is realized miscellaneous MIBK
Largely conversion obtains MIBK Synthesis liquids to matter；
(ii) enter cut light tower after MIBK Synthesis liquids separation hydrogen and carry out extracting rectifying, removed overhead light component, tower bottoms
Phase logistics enters acetone recovery tower；
(iii) the tower reactor liquid phase stream of (ii) step is through acetone recovery tower extracting rectifying, in the unreacted acetone of recovered overhead, tower reactor
Liquid phase stream obtains the logistics of rich aqueous phase and the logistics rich in organic phase after phase separation；
(iv) logistics of rich aqueous phase enters technique water tower, tower top obtain boiling point be less than MIBK/ water azeotropic mixtures organic matter and
The azeotropic mixture of MIBK/ water enters dehydrating tower, and tower bottoms part enters cut light tower, or cut light tower and acetone recovery tower；
(v) logistics rich in organic phase and process water column overhead stream enter dehydrating tower, and dehydrating tower is dividing wall column, technique water tower
Overhead stream enters from dehydrating tower side, and the logistics rich in organic phase enters from the public stripping section of dehydrating tower, and dehydrating tower is another
Liquid-liquid quantizer is set on the column plate of side, side line obtains the water/alcohol distillate for being substantially free of MIBK close to water/alcohol azeotropic composition,
Removed overhead acetone, methanol, tower reactor obtain substantially free of water liquid phase stream；
(vi) dehydrating tower tower reactor liquid phase stream enters dealcoholysis tower, and in removed overhead impurity alcohols, tower reactor obtains thick MIBK and distillates
Thing enters MIBK treating columns, removed overhead light component, side take-off MIBK products after refining.
2. according to the method described in claim 1, it is characterized in that, the industrial by-product waste liquid acetone comes from conjugated oxidation ring
The acetone of Ethylene Oxide/tert-butyl alcohol combined production device by-product, based on waste liquid acetone weight, it includes water 0.1wt%~5wt%, methanol
0.5wt%~6wt%, epoxy iso-butane 1wt%~20wt%, acetone 60wt%~95wt%, isopropanol 0.01wt%~
0.5wt%, methyl ethyl ketone 0.01wt%~0.2wt%, tert-butyl alcohol 1wt%~15wt%, aldehydes 0.01wt%~2wt%, ethers
0.01wt%~5wt%.
3. method according to claim 1 or 2, it is characterised in that 45~75wt% is included in the MIBK Synthesis liquids
Acetone, the water of the MIBK of 18~35wt%, 4~10wt%, the isopropanol of 0.01~2wt%, the diacetone alcohol of 0~1wt%,
The diisobutyl ketone of 0.1~2wt%, 0.01~2wt% iso-butanes, the 2- methylpentanes of 0.001~0.5wt%, 0.01~
The methanol of 6wt%, the tert-butyl alcohol of 0~8wt%, the isobutylaldehyde of 0.1~15wt%, the isobutanol of 0.01~15wt%, and
The methyl ethyl ketone of 0.01~0.2wt% and the ethers of 0.01~5wt%.
4. according to the method described in claim 1, it is characterized in that, cut light tower and acetone recovery tower are extractive distillation columns,
One or more of the extractant in monoethanolamine, ethylene glycol, hexylene glycol and water, preferably water take off light component as extractant
The Solvent quantity of tower is 0.05~5 with the mass ratio of waste liquid acetone:1, preferably 0.1~3:1, the extractant of acetone recovery tower is used
The mass ratio of amount and feeding liquid is 0~5:1, preferably 0~3:1.
5. according to the described method of any one of claim 1-4, it is characterised in that the theoretical cam curve of the dehydrating tower is
20~80 pieces, preferably 20~60 pieces；The theoretical cam curve of public rectifying section account for dehydrating tower theoretical tray sum 5~50%, it is excellent
Select 10~30%；Boiling point is less than top at the organic matter of MIBK/ water azeotropic mixtures and MIBK/ water azeotropic mixture chargings and public rectifying section
Theoretical cam curve between lower end accounts for 5~30%, preferably the 10~25% of dehydrating tower theoretical tray sum；Boiling point is less than MIBK/
Theoretical cam curve at the organic matter of water azeotropic mixture and MIBK/ water azeotropic mixture chargings between lower section and public stripping section upper end accounts for de-
10~50%, preferably the 11~35% of water tower theoretical tray sum；At side take-off between top and public rectifying section lower end
Theoretical cam curve accounts for 10~50%, preferably the 11~35% of dehydrating tower theoretical tray sum；Lower section is carried with public at side take-off
Evaporate the theoretical cam curve between section upper end accounts for dehydrating tower theoretical tray sum 5~30%, preferably 10~25%；Public stripping section
Theoretical cam curve account for dehydrating tower theoretical tray sum 5~50%, preferably 20~40%.
6. according to the method any one of claim 1-5, it is characterised in that the dehydrating tower side column plate upper liquid-
Filling filler in liquid quantizer, the filler include filler A and B, and wherein filler A is modified super hydrophilic metal packing, filler B
For modified super oleophylic metal packing, filler A is seated in lower floor, and filler B is seated in upper strata, filler A and filler B filling height ratios
For 1:8~4:1, preferably 1:4~2:1.
7. according to the method described in claim 6, it is characterized in that, filler A is the solution that metal packing is put into strong oxidizing property
In carry out 12~18h of processing, rinsed to neutrality obtain with water afterwards, the preferred potassium bichromate sulfuric acid of solution of the strong oxidizing property
Solution and/or potassium permanganate sulfuric acid solution.
8. the method according to claim 6 or 7, it is characterised in that the filler B passes through on filler A surface sprayings
Surface modifier and auxiliary agent, heating 30min~60min is obtained at 200~300 DEG C, wherein, the preferred polytetrafluoro of surface modifier
Vac emulsion, the addition of the preferred sulfonated polyimide lotion of auxiliary agent, wherein ptfe emulsion and sulfonated polyimide lotion
Mass ratio is 1:1~20:1, preferably 5:1~10:1, the quality summation of surface modifier and auxiliary agent accounts for filler A mass
0.001%~1%, preferably 0.01~0.1%.
9. according to 1 or 4 the method for claim, it is characterised in that the cut light tower in 80~300KPaA of pressure,
It is preferred that operated under conditions of 100~200KPaA；Theoretical cam curve is 15~60, preferably 25~50；Feed entrance point is the 10th~30
Block plate, preferably the 15th~25 block of plate；Reflux ratio is 2~50, preferably 5~25, the addition of the coal addition position and feeding liquid of extractant
Position is identical or coal addition position higher than feeding liquid, preferably the 2nd~20 piece of theoretical plate.
10. according to 1 or 5 the method for claim, it is characterised in that dehydrating tower in 50~500KPaA of pressure, preferably 100~
Operated under conditions of 260KPaA；Reflux ratio is 1~30, preferably 5~15.
11. method according to claim 1, it is characterised in that dealcoholysis tower in 80~300KPaA of pressure, preferably 100~
Operated under conditions of 200KPaA；Theoretical cam curve is 15~55, preferably 20~40 blocks of plates；Feed entrance point is the 5th~35 block of plate,
It is preferred that the 15th~25 block of plate；Reflux ratio is 5~50, preferably 5~30.
12. method according to claim 1, it is characterised in that technique water tower is 50~200KPaA in pressure, preferably 80~
Operated under conditions of 160KPaA；Theoretical cam curve 5~30, preferably 10~25；Feed entrance point is the 2nd~20 block of plate, the preferably the 2nd
~15 blocks of plates；Reflux ratio is 0.1~10, preferably 1~5.
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| CN111672157A (en) * | 2020-06-28 | 2020-09-18 | 郑州铁路职业技术学院 | Method for realizing rapid extraction of organic compound |
| CN111921546A (en) * | 2020-07-30 | 2020-11-13 | 绍兴贝斯美化工股份有限公司 | Surface-hydrophobically-modified ketone alkylation catalyst and preparation method and application thereof |
| CN112266323A (en) * | 2020-10-28 | 2021-01-26 | 雅邦绿色过程与新材料研究院南京有限公司 | Process method for recovering acetone from waste liquid in production of epoxypropane and methyl tert-butyl ether |
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| CN113816834A (en) * | 2021-10-14 | 2021-12-21 | 北京化工大学 | Energy-saving rectification-adsorption combined method for preparing high-purity absolute ethyl alcohol |
| CN113816834B (en) * | 2021-10-14 | 2022-08-05 | 北京化工大学 | Energy-saving rectification-adsorption combined method for preparing high-purity absolute ethyl alcohol |
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