CN108503511B - By dimethyl adipate plus hydrogen system 1, the rectificating method of 6- hexylene glycol - Google Patents
By dimethyl adipate plus hydrogen system 1, the rectificating method of 6- hexylene glycol Download PDFInfo
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- CN108503511B CN108503511B CN201810519363.4A CN201810519363A CN108503511B CN 108503511 B CN108503511 B CN 108503511B CN 201810519363 A CN201810519363 A CN 201810519363A CN 108503511 B CN108503511 B CN 108503511B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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Abstract
The present invention relates to one kind to add hydrogen system 1 by dimethyl adipate, the crude product rectificating method of 6- hexylene glycol, the method includes two stages of continuous rectification and batch fractionating, the continuous rectification stage includes three continuous rectification apparatus interconnected again, these three continuous rectification apparatus include tower body, and tower body bottom temp increases step by step, rectifying raw material of the tower bottoms of the above tower body bottom as next tower body every time.The batch fractionating stage includes a batch rectification device, which includes tower body and heating kettle.The heating kettle is used to collect the distillate at the top of the second continuous rectification apparatus tower body, batch rectification is carried out to the distillation, the distillate is added in heating kettle, it is gradually heated up vaporization again, from the steam of tower body Base top contact after condensing, a part is as distillating liquid product, another part is sent back in tower as reflux, it after the liquid of kettle to be heated reaches prescribed requirement, is recycled and is used to add hydrogen system 1, in the reaction step of 6- hexylene glycol.
Description
Technical field
The present invention relates to the proposition fields of chemically synthesized product, more particularly to one kind is for adding hydrogen system by dimethyl adipate
The rectificating method of 1,6- hexylene glycol.
Background technique
1,6- hexylene glycol, English name 1,6-hexanediol(HDO), molecular formula C6H14O2, 42 DEG C of fusing point, boiling point 250
DEG C, it is a kind of fine chemical material, unique properties have in UV coating, polyester, polyurethane, plasticizer, pesticide and medicine
It is more and more widely used.There are two terminal hydroxy group, this structures can preferably participate in polymerization reaction, while 1 for 1,6- hexylene glycol,
The carbochain of 6- hexylene glycol is longer, can effectively improve the mechanical strength of polymer.In terms of fuel and polyester, 1,6- hexylene glycol
The color and adsorption capacity of product are improved, and there is good photostability.1,6-HD is also widely used in
In polyurethane field, it can effectively improve the hydrolytic resistance and mechanical strength of product.Therefore, 1,6- hexylene glycol is known as organic
The new foundation stone of synthesis.
China is increasing the demand of 1,6- hexylene glycol rapidly, wherein there is larger proportion dependent on import.Currently, international
There are German BASF, Lang Sheng, Ube etc. in upper main 1,6- hexylene glycol production company, and China only has a small number of producers that can lack
Amount production, and process for producing is also in growth stage.In order to make up China in the vacancy of preparation 1,6- hexylene glycol technique, need
Develop a set of efficient 1,6-HD preparation process and purification technique.About the preparation process of 1,6- hexylene glycol, have
Many patent disclosure mistakes, our company also develop the catalyst and work that 1,6- hexanedioic acid dialkyl ester adds hydrogen preparation 1,6- hexylene glycol
Skill scheme.But the report of the rectifying purifying process about 1,6-HD is simultaneously few.BASF AG's U.S. Patent application
US5981769A and Chinese patent application CN1484627A, UBE Industries Ltd. CN102186798A are once disclosed oneself
The preparation and method of purification of glycol, these methods are mainly the pair for utilizing cyclohexane oxidation to generate during cyclohexanone/cyclohexanol
Product -- mixture of carboxylic acids is that mixed acid ester, right back end hydrogenation is made in raw material, and rectifying obtains 1,6- hexylene glycol.The original that this method uses
Material is mixed acid (including a variety of organic acids), obtains mixed ester (comprising a variety of esters) by esterification, then hydrogenation reaction is raw
At mixed alcohol (contain a variety of alcohol), then rectifying and purification are carried out, relative to only with adipic acid being that raw material generates hexanedioic acid dialkyl ester,
Right back end hydrogenation obtains the technique of hexylene glycol, the former preparation process is complicated, and impurity and various products are numerous, and purification difficulty is big, produces eventually
Object purity is difficult to ensure and equipment investment is big.
Chinese invention patent CN 102351648A discloses the method for purification of 1,6- hexylene glycol, comprising: hydrogenation reaction produces
Object is introduced into pre-distillation column, distills out methanol；It is further that the mixed liquor that the pre-distillation column tower reactor comes out enters caprolactone tower body
Separating-purifying obtains caprolactone product and 1,6- hexylene glycol crude liquid；The 1,6-HD crude liquid enters back into hexylene glycol treating column
Middle rectifying obtains 1,6- hexylene glycol product.Chinese invention patent CN 106748645A discloses the purification side of 1,6-HD
Method, comprising: ingredient and lower alcohol that boiling point is lower than water are separated by the rectifying of the 1st stage using the method for segmentation rectifying；Pass through
The rectifying of 2nd stage, separation boiling point are higher than the esters of hexylene glycol；By the rectifying in the 3rd stage, further separate boiling point lower than oneself two
The lactone component of alcohol.
It can be seen that for 1, the rectification and purification technique of 6- hexylene glycol or it is raw material composition too complex and leads to essence
Evaporate purifying technique complexity, product purity is limited simultaneously or is that disclosure is less not to the condition of rectifying and requirement progress
It is described in detail.
Summary of the invention
In order to solve the above problem of the prior art, the present invention provides a kind of for adding hydrogen system 1,6- by dimethyl adipate
The crude product that dimethyl adipate is hydrogenated to can be carried out rectification and purification using the method by the rectificating method of hexylene glycol, point
The substances such as methanol, light oil, ester type compound, 1,6-HD, heavy oil are not obtained.Using this method, not only purifying technique is simple,
And be important to, be based on this rectification and purification method, can obtain methanol of the purity greater than 99.90% and 1,6- greater than 99.80% oneself two
Alcohol.
In order to achieve the above object, the main technical schemes that the present invention uses are as follows:
The present invention provides a kind of crude product rectifier unit of hexylene glycol Han 1,6-, includes the first continuous rectification interconnected
Device, the second continuous rectification apparatus and third continuous rectification apparatus, and connect with second continuous rectification apparatus the 4th between
It has a rest rectifier unit, aforementioned each rectifier unit separately includes tower body;4th batch rectification device also includes set on tower body bottom
Heating kettle；The thick production of the hexylene glycol Han 1,6- according to the tower body bottom temp of first, second, third continuous rectification apparatus
The boiling point temperature range of object steps up；
Feed inlet is equipped in the middle part of the side of the tower body of first continuous rectification apparatus, first continuous rectification apparatus
Tower body outlet at bottom connects the feed inlet in the middle part of the tower body side of second continuous rectification apparatus, the second continuous rectification dress
The tower body outlet at bottom set connects the feed inlet in the middle part of the tower body side of the third continuous rectification apparatus；Second continuous fine
The tower body top exit of distillation unit connects the feed inlet of the heating kettle of the 4th batch rectification device, makes second continuous fine
Water, light oil and the ester type compound that the tower body top exit of distillation unit comes out are in the heating kettle of the 4th batch rectification device
It is heated vaporization, isolates water and light oil from tower body top, remaining ester type compound passes through the heating kettle in the heating kettle
Discharge gate is connected to plus hydrogen system 1, the reaction kettle or storage tank of 6- hexylene glycol.
Preferably, the heating kettle comprising autoclave body and is set to the intracorporal heating device of kettle, second continuous rectification apparatus
The material isolated of tower body top exit be collected into the autoclave body.
Preferably, the tower body of first continuous rectification apparatus is atmospheric tower, and the feed inlet of the tower body is located at tower body
Height from bottom to up 10/50 ~ 30/50 position；The tower body head temperature is 60-70 DEG C, and the tower body bottom is equipped with tower reactor,
Bottom temperature is 80-180 DEG C.
Preferably, the tower body of second continuous rectification apparatus is vacuum tower, and the feed inlet of the tower body is located at tower body
Height from bottom to up 15/50 ~ 30/50 position；The tower body head temperature is 100-180 DEG C, and the tower body bottom is equipped with tower
Kettle, bottom temperature are 120-220 DEG C, and the vacuum degree inside the tower body is absolute pressure≤50KPa.
Preferably, the tower body of the third continuous rectification apparatus is vacuum tower, and the feed inlet of the tower body is located at tower body
Height from bottom to up 15/50 ~ 35/50 position；The tower body head temperature is 120-220 DEG C, and the tower body bottom is equipped with tower
Kettle, bottom temperature are 150-240 DEG C, and the vacuum degree inside the tower body is absolute pressure≤20KPa.
Preferably, the tower body of the 4th batch rectification device is vacuum tower, and the feed inlet of the tower body is located at tower body
Height from bottom to up 10/50 ~ 30/50 position；The tower body head temperature is 0-100 DEG C, and the heating temperature in the kettle is
120-220 DEG C, the vacuum degree inside the tower body is absolute pressure≤50KPa.
Preferably, first, second, third continuous rectification apparatus and the 4th batch rectification device separately include condensation
The tower body top exit of device, each rectifier unit connects the condenser, is passed through refrigerant in the condenser, is distinguished by heat exchange
By the distillation condensation of output at the top of each tower body, a part becomes condensation distillate, and a part is back in tower body.
It preferably, include heat exchanger, the heat exchange in the tower reactor of first, second, third continuous rectification apparatus
High temperature heating agent is passed through in device, by high temperature heating agent to the material heated at constant temperature collected in tower reactor, make material evaporation enter with it is corresponding
Tower body in, by stripping and rectifying in uphill process.
The present invention also provides one kind to add hydrogen system 1 by dimethyl adipate, the crude product rectificating method of 6- hexylene glycol, oneself two
Dimethyl phthalate adds hydrogen system 1, and after the completion of 6- hexylene glycol reaction step, product is to include methanol, water, light oil, ester type compound, 1,6-
The thick hexylene glycol mixture of hexylene glycol and heavy oil；Wherein, described the method includes two stages of continuous rectification and batch fractionating
The continuous rectification stage includes the first continuous rectification apparatus interconnected, the second continuous rectification apparatus and third continuous rectification dress
It sets, aforementioned each continuous rectification apparatus is respectively provided with tower body;
Thick hexylene glycol mixture charging in the middle part of the tower body of first continuous rectification apparatus, from tower body top exit
Methanol continuously is isolated, tower body bottoms material is continuously discharged from tower body outlet at bottom；The tower body of first continuous rectification apparatus
Bottoms material is fed continuously and feeds in the middle part of the tower body of second continuous rectification apparatus, continuously divides from tower body top exit
Water, light oil and ester type compound that boiling point is higher than methanol are separated out, water, light oil and ester type compound herein is collected, from
Tower body bottoms material is continuously discharged in tower body outlet at bottom；The tower body bottoms material of second continuous rectification apparatus is fed continuously
And fed in the middle part of the tower body of the third continuous rectification apparatus, hexylene glycol, tower body bottom are continuously isolated from tower body top exit
The heavy oil component in portion is discharged；
The tower body of first continuous rectification apparatus is atmospheric tower, and the feed inlet of the tower body is located at tower body height under
Supreme 10/50 ~ 30/50 position；The tower body head temperature is 60-70 DEG C, and the tower body bottom is equipped with tower reactor, bottom temperature
It is 80-180 DEG C；
The tower body of second continuous rectification apparatus is vacuum tower, and the feed inlet of the tower body is located at tower body height under
Supreme 15/50 ~ 30/50 position；The tower body head temperature is 100-180 DEG C, and the tower body bottom is equipped with tower reactor, tower reactor temperature
Degree is 120-220 DEG C, and the vacuum degree inside the tower body is absolute pressure≤50Kpa；
The tower body of the third continuous rectification apparatus is vacuum tower, and the feed inlet of the tower body is located at tower body height under
Supreme 15/50 ~ 35/50 position；The tower body head temperature is 120-220 DEG C, and the tower body bottom is equipped with tower reactor, tower reactor temperature
Degree is 150-240 DEG C, and the vacuum degree inside the tower body is absolute pressure≤20Kpa；
The batch fractionating includes the 4th batch rectification device, and the 4th batch rectification device is comprising tower body and is set to tower
The heating kettle of body bottom, water, light oil and the esters chemical combination that will be collected from the tower body top exit of second continuous rectification apparatus
Object imports in the heating kettle of the 4th batch rectification device, heats and vaporizes, and isolates water and light oil from tower body top；Heating
Raffinate is ester type compound in kettle, is fed back to as raw material plus hydrogen system 1, the reaction step of 6- hexylene glycol recycle；
The tower body of 4th batch rectification device is vacuum tower, and the feed inlet of the tower body is located at tower body height under
Supreme 10/50 ~ 30/50 position；The tower body head temperature is 0-100 DEG C, and the heating temperature in the kettle is 120-220 DEG C,
Vacuum degree inside the tower body is absolute pressure≤50KPa.
The position that tower body feed inlet about each rectifier unit is arranged, according to the height of tower body and the difference of total column plate quantity
And it is different.For example, when the specific implementation total number of plates of tower body used is 50 column plates, the tower body of the first continuous rectification apparatus
Feed inlet is located between 10-30 block column plate from bottom to up, similarly when total number of plates of tower body is 100 column plates, first
The feed inlet of the tower body of continuous rectification apparatus is located between 20-60 block column plate from bottom to up.The tower body of other each rectifier units
Position is arranged in feed inlet, and all the rest may be inferred.
The tower body feed inlet of each rectifier unit is located in the middle part of tower body side or middle and lower part, it is ensured that stripping section and rectifying section
Optimal spatial proportion, guarantee that material has enough spaces to carry out gas-liquid exchange respectively in the rectifying section and stripping section of tower body.In
When designing the position of feed inlet, be distillated the substantially content range of each component, density of fraction, tower reactor temperature in material can be comprehensively considered
Each factors such as degree, or determined by rectifying experiment.
The beneficial effects of the present invention are:
One kind through the invention adds hydrogen system 1 by dimethyl adipate, and the rectifier unit and method of 6- hexylene glycol carry out oneself
The rectifying of glycol crude product, can be completely separable by methanol, light oil, ester type compound, hexylene glycol, heavy oil, obtain purity >=
99.90% methanol, the hexylene glycol of purity >=99.80%, while ester type compound can be recycled completely, reduce pollution
The discharge of object.
Rectifier unit of the present invention is using three continuous rectification apparatus and a batch rectification device to the thick production containing hexylene glycol
Object carries out rectifying, purification.The ester type compounds such as the caprolactone and dimethyl adipate of the batch rectification device output, can be direct
Feed back to previous step adds hydrogen system 1, and (initial temperature with higher) is recycled in the processing step of 6- hexylene glycol, guarantees
Ester type compound recycles completely, saves raw material materials, energy consumption, and reduce the production cost of hexylene glycol.
Detailed description of the invention
Fig. 1 adds hydrogen system 1, the schematic diagram of the rectifier unit of 6- hexylene glycol by dimethyl adipate for the present invention.
[description of symbols]
The first continuous rectification apparatus of 1-, 11- tower body, 12- tower reactor, the second continuous rectification apparatus of 2-, 21- tower body, 22- tower
Kettle, 3- third continuous rectification apparatus, 31- tower body, 32- tower reactor, the 4th batch rectification device of 4-, 41- tower body, 42 heating kettles.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair
It is bright to be described in detail.
The purpose of the present invention is using dimethyl adipate to adding the crude product of hydrogen 1,6-HD rectifying and mention
Pure, and dimethyl adipate adds hydrogen system 1, the weight composition of the crude product of 6- hexylene glycol is as follows: methanol 20-35%, water 0.01-5%,
Light oil (the boiling point impurity lower than caprolactone higher than methanol) 0.01-10%, other ester type compounds (caprolactone etc.) 0.01-5%, oneself
Acid dimethyl 0.01-40%, 1,6- hexylene glycol 40-67%, heavy oil (the boiling point impurity higher than hexylene glycol) 0.01-10%, it is aforementioned each
Component boiling point is successively to increase.It is formed based on above material, the present invention devises a set of rectificating method and device.
The method is summarized are as follows: including two stages of continuous rectification and batch fractionating, the continuous rectification stage includes again
Three continuous rectification apparatus interconnected, these three continuous rectification apparatus include tower body, and tower body bottom temp rises step by step
Height, every time rectifying raw material of the tower bottoms of the above tower body bottom as next tower body.The batch fractionating stage packet
Containing a batch rectification device, which includes tower body and heating kettle.It is continuous for collecting second in the heating kettle
Distillate at the top of the tower body of rectifier unit carries out batch rectification to the product that the part distills out: being added in heating kettle, then by
Gradually heating vaporization, from the steam of tower body Base top contact after condensing, a part is as liquid product is distillated, and another part is as reflux
Send back in tower, after the liquid of kettle to be heated composition reaches specified value, discharge it and be transported to plus hydrogen system 1,6- hexylene glycol it is anti-
It answers in process and is used as feedstock circulation.
It is as shown in connection with fig. 1 the present invention plus hydrogen system 1, the schematic diagram of the crude product rectifier unit of 6- hexylene glycol, specific essence
Evaporate process, material trend and operating condition are as follows:
The tower body 11 of first continuous rectification apparatus 1 be atmospheric tower, and the feed inlet of tower body 11 be located at tower body height from down toward
Upper 10/50 ~ 30/50 position.11 head temperature of tower body is 60-70 DEG C, and the tower body bottom is equipped with tower reactor 12, temperature in tower reactor 12
Degree is 80-180 DEG C.The thick hexylene glycol mixture is fed in the middle part of the tower body 11 of the first continuous rectification apparatus 1, from tower body top
Continuously isolate the methanol of high-purity in outlet.
The tower body 21 of second continuous rectification apparatus 2 is vacuum tower, and the feed inlet of tower body 21 is located at tower body height from bottom to up
15/50 ~ 30/50 position.21 head temperature of tower body is 100-180 DEG C, and 21 bottom of tower body is equipped with tower reactor 22, temperature in tower reactor 22
It is 120-220 DEG C.Vacuum degree inside tower body 11 is absolute pressure≤50KPa.The tower reactor 12 of first continuous rectification apparatus 1 is continuously discharged
Material be fed continuously, and feed in the middle part of the tower body 21 of the second continuous rectification apparatus 2, continuously divide from 21 top exit of tower body
Water, light oil and ester type compound that boiling point is higher than methanol are separated out, water, light oil and ester type compound herein is collected.
The tower body 31 of third continuous rectification apparatus 3 is vacuum tower, and the feed inlet of tower body 31 is located at tower body height from bottom to up
15/50 ~ 35/50 position.31 head temperature of tower body is 120-220 DEG C, and 31 bottom of tower body is equipped with tower reactor 32, and 32 temperature of tower reactor is
150-240℃.Vacuum degree inside tower body 31 is absolute pressure≤20KPa.The tower reactor 22 of the tower body 21 of second continuous rectification apparatus 2 connects
The material of continuous discharge is fed continuously, and is fed in the middle part of the tower body of third continuous rectification apparatus 3 31, from 31 top exit of tower body
Continuously isolate hexylene glycol, the heavy oil component discharge of 31 bottom of tower body.
The tower body 41 of 4th batch rectification device 4 is vacuum tower, and the feed inlet of tower body 41 is located at tower body height from bottom to up
10/50 ~ 30/50 position.41 head temperature of tower body is 0-100 DEG C, and temperature is 120-220 DEG C in heating kettle 42.In tower body 41
The vacuum degree in portion is absolute pressure≤50KPa.Boiling point is continuously isolated higher than methanol from 21 top of tower body of the second continuous rectification apparatus 2
Water, light oil and ester type compound be collected into the heating kettle 42 of the 4th batch rectification device 4, when in heating kettle 42 collect it is full
Afterwards, start rectifying: heating and vaporize, water and light oil are isolated at the top of tower body 41, the composition for measuring raffinate in heating kettle reaches
After the ester type compound of predetermined purity, this part ester type compound is fed back to as raw material and adds hydrogen system 1, the reaction of 6- hexylene glycol
Step cycle utilizes.
First, second, third continuous rectification apparatus 1,2,3 and the 4th batch rectification device 4 also include condenser respectively
80, the tower body top exit of each rectifier unit connects the condenser 80, is passed through refrigerant in the condenser 80, passes through heat exchange
The distillation of output at the top of each tower body is condensed respectively, a part becomes condensation distillate, and a part is back to corresponding tower body
11, in 21,31.
It preferably, include heat exchange in the tower reactor 12,22,32 of first, second, third continuous rectification apparatus 1,2,3
Device 90 is passed through high temperature heating agent in the heat exchanger 90, by high temperature heating agent to the material constant temperature collected in tower reactor 12,22,32
Heating, make material evaporation enter in corresponding tower body 11,21,31, by stripping and rectifying in uphill process.
Continuous rectification apparatus
Continuous rectification: rectifying column contacts for vehicle repair major and carries out interphase mass transfer, and the condenser positioned at tower top obtains steam
Partial condensation, part lime set return to tower top as phegma, remaining distillate is overhead product.Tower reactor positioned at tower bottom makes liquid
Part vaporizes, and steam rises along tower, and remaining liquid is as bottom product.Charging is added in the middle part of tower, liquid in charging and
The liquid that upper tower segment comes declines along tower together, and the steam that the steam and lower tower section in charging come rises along tower together.In entire essence
It evaporates in tower, vehicle repair major counter current contacting, carries out interphase mass transfer.Volatile components in liquid phase enter vapour phase, and the difficulty in vapour phase is waved
Hair component is transferred to liquid phase.Distillate by be high-purity volatile components, tower bottom product by be high-purity difficult volatile component.Into
Tower section more than material mouth, the further concentrate of volatile components in upflowing vapor, referred to as rectifying section；Feed inlet tower section below,
Volatile components, referred to as stripping section are extracted from dropping liq.The combination of two sections of operations, makes two components in liquid mixture
It is relatively completely separated, produces two kinds of products of required purity.Why continuous rectification can be such that liquid mixture obtains relatively completely
Separation, key be flow back application.Reflux includes that tower top high concentration volatile components liquid (after cooled) and tower bottom are high
Concentration difficulty volatile component steams both (being heated) gas and returns in tower, and the two vapour-liquid, which flows back, forms the vehicle repair major of counter current contacting,
Save a large amount of energy consumptions.
Batch rectification device
Batch fractionating is also known as batch rectification.When batch fractionating operation starts, whole materials are added in the heating kettle of rectifying column,
It is gradually heated up vaporization again, the steam come out from tower top is after condensing, and a part is as liquid product is distillated, and another part is as reflux
It sends back in tower, after liquid composition drops to specified value in kettle to be heated, by its primary discharge, then carries out the rectifying behaviour of next group
Make.Therefore, batch fractionating is compared with continuous rectification, and there are two features for tool: (1) batch fractionating is transient；(2) interval essence
It evaporates tower and there was only rectifying section.
Since the water, light oil and ester type compound amount that come out at the top of the tower body 21 of the second continuous rectification apparatus 2 are few and flow
It is small, therefore be adapted to recycle ester type compound therein using batch rectification device 4, be conducive to save energy consumption.
Scheme and technical effect in order to further illustrate the present invention, the following are be illustrated in connection with specific embodiments.
Embodiment 1
For the crude product after dimethyl adipate plus hydrogen, the i.e. raw material of rectifying, weight composition is as follows: methanol:
35.0%；Water: 0.2%；Light oil (the boiling point impurity smaller than caprolactone): 0.3%；
Other ester type compounds (caprolactone etc.): 0.2%；Dimethyl adipate: 0.3%；1,6-HD: 63.8%；Heavy oil
(the boiling point impurity higher than hexylene glycol): 0.2%；It is formed based on material above-mentioned, has carried out rectifying separating experiment.
First continuous rectification apparatus is for recycling methanol, and pressure is absolute pressure 100KPa in the continuous rectification apparatus tower body, into
Material position is set in the 12nd block of column plate, and tower top temperature is 64.5 DEG C, and bottom temperature is 82.0 DEG C.Methanol is obtained from overhead collection
The purity of methanol is 99.95%, and kettle material enters the second continuous rectification apparatus.
Second continuous rectification apparatus is used for recycle-water, light oil and ester type compound, pressure in the continuous rectification apparatus tower body
For absolute pressure 35KPa, feed entrance point is located at the 16th block of column plate, and tower top temperature is 150 DEG C, and bottom temperature is 220 DEG C.Water, light oil and
For ester type compound (caprolactone and dimethyl adipate etc.) from overhead collection, kettle material enters third continuous rectification apparatus.
Third continuous rectification apparatus is for refining 1,6- hexylene glycol, and pressure is absolute pressure in the continuous rectification apparatus tower body
20KPa, feed entrance point are located at the 20th block of column plate, and tower top temperature is 180 DEG C, and bottom temperature is 240 DEG C.Hexylene glycol is received from tower top
Collection, the purity of obtained hexylene glycol are 99.88%, and heavy oil is discharged from tower reactor.
4th batch rectification device is for recycling ester type compound, and pressure is absolute pressure in the tower body of the rectifier unit of having a rest
50KPa, feed entrance point are located at the 12nd block of column plate, and tower top temperature is 120 DEG C, and the heating kettle temperature of bottom is 200 DEG C.Water and light oil
It is discharged from overhead extraction, ester type compound and from the discharge gate of heating kettle, as raw material for adding hydrogen hexylene glycol.
Embodiment 2
For the crude product after dimethyl adipate plus hydrogen, the i.e. raw material of rectifying, weight composition is as follows:
Methanol: 24.6%；Water: 2.5%；Light oil (the boiling point impurity smaller than caprolactone): 5.6%；
Other ester type compounds (caprolactone etc.): 2.2%；Dimethyl adipate: 18.0%；1,6-HD: 45.3%；Weight
Oily (the boiling point impurity higher than hexylene glycol): 1.8%；Based on forming based on material above-mentioned, rectifying separating experiment has been carried out.
First continuous rectification apparatus is for recycling methanol, and pressure is absolute pressure 100KPa in the continuous rectification apparatus tower body, into
Material position is set in the 25th block of column plate, and tower top temperature is 64.5 DEG C, and bottom temperature is 155 DEG C.Methanol is from overhead collection, obtained first
The purity of alcohol is 99.92%, and kettle material enters the second continuous rectification apparatus.
Second continuous rectification apparatus is used for recycle-water, light oil and ester type compound, pressure in the continuous rectification apparatus tower body
For absolute pressure 25KPa, feed entrance point is located at the 20th block of column plate, and tower top temperature is 165 DEG C, and bottom temperature is 212 DEG C.Water, light oil and
For ester type compound (caprolactone and dimethyl adipate etc.) from overhead collection, kettle material enters third continuous rectification apparatus.
Third continuous rectification apparatus is for refining 1,6- hexylene glycol, and pressure is absolute pressure in the continuous rectification apparatus tower body
10KPa, feed entrance point are located at the 32nd block of column plate, and tower top temperature is 173 DEG C, and bottom temperature is 236 DEG C.Hexylene glycol is received from tower top
Collection, the purity of obtained hexylene glycol are 99.82%, and heavy oil is discharged from tower reactor.
4th batch rectification device is for recycling ester type compound, and pressure is absolute pressure in the tower body of the rectifier unit of having a rest
40KPa, feed entrance point are located at the 18th block of column plate, and tower top temperature is 125 DEG C, and the heating kettle temperature of bottom is 215 DEG C.Water and light oil
It is discharged from overhead extraction, ester type compound and from the discharge gate of heating kettle, as raw material for adding hydrogen hexylene glycol.
Product methanol purity >=99.90% obtained by above embodiments, hexylene glycol purity >=99.80%, it was demonstrated that this work
Artistic skill is enough effectively to separate substance, and route is reasonable, and product purity is higher, the esters rate of recovery 99.5%, can directly use and add
In the reaction process of hydrogen hexylene glycol, so that the purification for product reduces energy consumption and cost.
Claims (1)
1. one kind adds hydrogen system 1, the crude product rectificating method of 6- hexylene glycol, in dimethyl adipate plus hydrogen system by dimethyl adipate
After the completion of 1,6- hexylene glycol reaction step, product is to include methanol, water, light oil, ester type compound, 1,6- hexylene glycol and heavy oil
Thick hexylene glycol mixture；It is characterized by:
The method includes two stages of continuous rectification and batch fractionating, the continuous rectification stage includes interconnected first
Continuous rectification apparatus, the second continuous rectification apparatus and third continuous rectification apparatus, aforementioned each continuous rectification apparatus are respectively provided with tower
Body;
Thick hexylene glycol mixture charging in the middle part of the tower body of first continuous rectification apparatus, it is continuous from tower body top exit
Methanol is isolated, tower body bottoms material is continuously discharged from tower body outlet at bottom；The tower body bottom of first continuous rectification apparatus
Material is fed continuously and feeds in the middle part of the tower body of second continuous rectification apparatus, continuously isolates from tower body top exit
Boiling point is higher than water, light oil and the ester type compound of methanol, is collected to water, light oil and ester type compound herein, from tower body
Tower body bottoms material is continuously discharged in outlet at bottom；The tower body bottoms material of second continuous rectification apparatus be fed continuously and from
Charging, continuously isolates hexylene glycol from tower body top exit in the middle part of the tower body of the third continuous rectification apparatus, tower body bottom
Heavy oil component discharge；
The tower body of first continuous rectification apparatus is atmospheric tower, and the feed inlet of the tower body is located at tower body height from bottom to up
10/50 ~ 30/50 position；The tower body head temperature is 60-70 DEG C, and the tower body bottom is equipped with tower reactor, and bottom temperature is
80-180℃；
The tower body of second continuous rectification apparatus is vacuum tower, and the feed inlet of the tower body is located at tower body height from bottom to up
15/50 ~ 30/50 position；The tower body head temperature is 100-180 DEG C, and the tower body bottom is equipped with tower reactor, and bottom temperature is
120-220 DEG C, the vacuum degree inside the tower body is absolute pressure≤50Kpa；
The tower body of the third continuous rectification apparatus is vacuum tower, and the feed inlet of the tower body is located at tower body height from bottom to up
15/50 ~ 35/50 position；The tower body head temperature is 120-220 DEG C, and the tower body bottom is equipped with tower reactor, and bottom temperature is
150-240 DEG C, the vacuum degree inside the tower body is absolute pressure≤20Kpa；
The batch fractionating includes the 4th batch rectification device, and the 4th batch rectification device is comprising tower body and is set to tower body bottom
The heating kettle in portion leads water, light oil and the ester type compound collected from the tower body top exit of second continuous rectification apparatus
It in the heating kettle for entering the 4th batch rectification device, heats and vaporizes, isolate water and light oil at the top of the tower body, in heating kettle
Raffinate is ester type compound, is fed back to as raw material plus hydrogen system 1, the reaction step of 6- hexylene glycol recycle；
The tower body of 4th batch rectification device is vacuum tower, and the feed inlet of the tower body is located at tower body height from bottom to up
10/50 ~ 30/50 position；The tower body head temperature is 0-100 DEG C, and the heating temperature in the kettle is 120-220 DEG C, described
Vacuum degree inside tower body is absolute pressure≤50KPa.
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| CN102351648B (en) * | 2011-09-09 | 2013-11-20 | 上海戊正工程技术有限公司 | Process for producing 1,6-hexanediol and coproducing epsilon-caprolactone |
| CN105061152A (en) * | 2015-08-17 | 2015-11-18 | 抚顺华东能源科技研发有限公司 | Process and device for preparing 1,6-hexanediol |
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