CN108503511A - By dimethyl adipate Hydrogenation 1, the distillation system and method for 6- hexylene glycols - Google Patents
By dimethyl adipate Hydrogenation 1, the distillation system and method for 6- hexylene glycols Download PDFInfo
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- CN108503511A CN108503511A CN201810519363.4A CN201810519363A CN108503511A CN 108503511 A CN108503511 A CN 108503511A CN 201810519363 A CN201810519363 A CN 201810519363A CN 108503511 A CN108503511 A CN 108503511A
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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 a kind of rectificating method and systems, the method includes two stages of continuous rectification and batch fractionating, the continuous rectification stage includes three continuous rectification apparatus being connected with each other 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 after the steam of tower body Base top contact is condensed, a part is used as and distillates liquid product, another part is sent back to as reflux in tower, after the liquid of kettle to be heated reaches prescribed requirement, recycled in the reaction step for 1,6 hexylene glycol of Hydrogenation.
Description
Technical field
The present invention relates to the proposition fields of chemically synthesized product, more particularly to one kind is for by dimethyl adipate Hydrogenation
The rectificating method of 1,6- hexylene glycol.
Background technology
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 polymerisation, while 1 for 1,6- hexylene glycol,
The carbochain of 6- hexylene glycols is longer, can effectively improve the mechanical strength of polymer.In terms of fuel and polyester, 1,6- hexylene glycol
The color and luster 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 glycols are known as organic
The new foundation stone of synthesis.
The demand in China pair 1,6- hexylene glycols is increasing rapidly, wherein there is larger proportion to depend on import.Currently, international
Upper main 1,6- hexylene glycols production company has German BASF, Lang Sheng, Ube etc., China to only have 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 for preparing 1,6- hexylene glycol techniques, need
Develop a set of efficient 1,6-HD preparation process and purification technique.About the preparation process of 1,6- hexylene glycols, have
Many patent disclosure mistakes, our company also develop 1,6- hexanedioic acid dialkyl esters Hydrogenation for the catalyst and work of 1,6- hexylene glycols
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 of glycol and method of purification, these methods are mainly the pair generated using cyclohexane oxidation 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 glycols.The original that this method uses
Material is mixed acid（Including a variety of organic acids）, mixed ester is obtained by esterification（Including a variety of esters）, then hydrogenation reaction life
At mixed alcohol（Containing 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,
So 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 disclose the method for purification of 1,6- hexylene glycols, including：Hydrogenation reaction is produced
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, the thick liquid of 6- hexylene glycols；The thick liquid of 1,6-HD enters back into hexylene glycol treating column
Middle rectifying obtains 1,6- hexylene glycol products.Chinese invention patent CN 106748645A disclose the purification side of 1,6-HD
Method, including：Using the method for segmentation rectifying, by the rectifying of the 1st stage, separation boiling point is less than the ingredient and lower alcohol of water；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 detach boiling point less than oneself two
The lactone component of alcohol.
It can be seen that for 1, the rectification and purification technique of 6- hexylene glycols or it is raw material composition too complex and leads to essence
It evaporates that purifying technique is complicated while product purity is limited or to be that disclosure is less to the condition of rectifying and requires progress
It is described in detail.
Invention content
In order to solve the above problem of the prior art, the present invention provides a kind of for by dimethyl adipate Hydrogenation 1,6-
The crude product that dimethyl adipate is hydrogenated to can be carried out rectification and purification by the distillation system of hexylene glycol using this system, point
The substances such as methanol, light oil, ester type compound, 1,6-HD, heavy oil are not obtained.The invention further relates to corresponding rectificating method,
Using this method, not only purifying technique is simple, and is important to, and is based on this rectification and purification method, can obtain purity and be more than 99.90%
Methanol and 1,6-HD more than 99.80%.
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 distillation system of the hexylene glycol Han 1,6-, including the first continuous rectification dress being connected with each other
It sets, the second continuous rectification apparatus and third continuous rectification apparatus, and the 4th interval being connect with second continuous rectification apparatus
Rectifier unit, aforementioned each rectifier unit separately include tower body;4th batch rectification device also includes set on tower body bottom
Heating kettle；The crude product of the hexylene glycol Han 1,6- according to the tower body bottom temp of first, second, third continuous rectification apparatus
Boiling point temperature range step up；
Feed inlet, the tower body of first continuous rectification apparatus are equipped in the middle part of the side of the tower body of first continuous rectification apparatus
Outlet at bottom connects the feed inlet in the middle part of the tower body side of second continuous rectification apparatus, second continuous rectification apparatus
Tower body outlet at bottom connects the feed inlet in the middle part of the tower body side of the third continuous rectification apparatus；The second continuous rectification dress
The tower body top exit set connects the feed inlet of the heating kettle of the 4th batch rectification device, and second continuous rectification is made to fill
Water, light oil and the ester type compound that the tower body top exit set comes out are added in the heating kettle of the 4th batch rectification device
Hot vapour isolates water and light oil, the discharge that remaining ester type compound passes through the heating kettle in the heating kettle from tower body top
Mouth is connected to Hydrogenation 1, the reaction kettle or storage tank of 6- hexylene glycols.
Preferably, the heating kettle includes autoclave body and the heating device in autoclave body, 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 include respectively 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.
Preferably, in the tower reactor of first, second, third continuous rectification apparatus include heat exchanger, the heat exchange
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 by dimethyl adipate Hydrogenation 1, the crude product rectificating method of 6- hexylene glycols, oneself two
Dimethyl phthalate Hydrogenation 1, after the completion of 6- hexylene glycol reaction steps, 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, the second continuous rectification apparatus and third the continuous rectification dress being connected with each other
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, 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 is fed in the middle part of the tower body of second continuous rectification apparatus, is continuously isolated 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, hexylene glycol is continuously isolated 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 is discharged；
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, water and light oil are isolated from tower body top；In heating kettle
Raffinate is ester type compound, is fed back to Hydrogenation 1 as raw material, the reaction step of 6- hexylene glycols recycles.
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.
The position that tower body feed inlet about each rectifier unit is arranged, according to the difference of the height and total column plate quantity of tower body
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 blocks 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 blocks column plate from bottom to up.The tower body of other each rectifier units
All the rest may be inferred for feed inlet installation position.
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 proportioning, ensure that material has enough space to carry out gas-liquid exchange respectively in the rectifying section and stripping section of tower body.
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 considered
Each factors such as degree, or determined by rectifying experiment.
The beneficial effects of the invention are as follows：
One kind through the invention carries out hexylene glycol by dimethyl adipate Hydrogenation 1, the distillation system and method for 6- hexylene glycols
The rectifying of crude product, can be completely separable by methanol, light oil, ester type compound, hexylene glycol, heavy oil, obtains purity >=99.90%
Methanol, the hexylene glycol of purity >=99.80%, while ester type compound can be recycled completely, reduce the row of pollutant
It puts.
Distillation system 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
The Hydrogenation 1 of previous step is fed back to, is recycled in the processing step of 6- hexylene glycols（There is higher initial temperature）, ensure
Ester type compound recycles completely, saves raw material materials, energy consumption, and reduce the production cost of hexylene glycol.
Description of the drawings
Fig. 1 is the present invention by dimethyl adipate Hydrogenation 1, the schematic diagram of the distillation system of 6- hexylene glycols.
【Reference sign】
The first continuous rectification apparatus of 1-, 11- tower bodies, 12- tower reactors, the second continuous rectification apparatus of 2-, 21- tower bodies, 22- tower reactors, 3-
Third continuous rectification apparatus, 31- tower bodies, 32- tower reactors, the 4th batch rectification devices of 4-, 41- tower bodies, 42 heating kettles.
Specific implementation mode
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by specific implementation mode, to this hair
It is bright to be described in detail.
The purpose of the present invention is carry out rectifying to the crude product using dimethyl adipate Hydrogenation 1,6-HD and carry
It is pure, and dimethyl adipate Hydrogenation 1, the weight composition of the crude product of 6- hexylene glycols are 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-HD 40-67%, heavy oil（The boiling point impurity higher than hexylene glycol）0.01-10%, it is aforementioned each
Component boiling point is to increase successively.It is formed based on above material, the present invention devises a set of rectificating method and system.
The method is summarised as：Including two stages of continuous rectification and batch fractionating, the continuous rectification stage includes again
Three continuous rectification apparatus being connected with each other, 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：It is added in heating kettle, then by
Gradually heating vaporization, from after the steam of tower body Base top contact is condensed, 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 Hydrogenation 1,6- hexylene glycols it is anti-
It answers in process and is used as feedstock circulation.
It show Hydrogenation 1 of the present invention, the schematic diagram of the crude product distillation system of 6- hexylene glycols, specific essence in conjunction with Fig. 1
Evaporating process, material trend and operating condition is：
The tower body 11 of first continuous rectification apparatus 1 is atmospheric tower, and the feed inlet of tower body 11 is located at tower body height from bottom to up 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, and temperature is in tower reactor 12
80-180℃.The thick hexylene glycol mixture is fed from 11 middle part of tower body of the first continuous rectification apparatus 1, from tower body top exit
The continuous methanol for isolating high-purity.
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 from the charging of the middle part of the tower body of the second continuous rectification apparatus 2 21, 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 from the 31 middle part charging of the tower body of third continuous rectification apparatus 3, from 31 top exit of tower body
It is continuous to 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, which is continuously isolated, from 21 top of tower body of the second continuous rectification apparatus 2 is higher than methanol
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：It heats and vaporizes, isolate water and light oil from 41 top of tower body, the composition for measuring raffinate in heating kettle reaches
After the ester type compound of predetermined purity, Hydrogenation 1, the reaction of 6- hexylene glycols are fed back to using this part ester type compound as raw material
Step cycle utilizes.
First, second, third continuous rectification apparatus 1,2,3 and the 4th batch rectification device 4 also include respectively condenser
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.
Preferably, in the tower reactor 12,22,32 of first, second, third continuous rectification apparatus 1,2,3 include heat exchange
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 makes steam obtain part
Condensation, part lime set return to tower top as phegma, remaining distillate is overhead product.Tower reactor positioned at bottom of tower makes liquid portion
Vaporization, steam rise along tower, and remaining liquid is as bottom product.Charging is added in the middle part of tower, the liquid in charging and upper tower
The liquid that section is come declines along tower together, and the steam that the steam and lower tower section in charging come rises along tower together.In entire rectifying column
In, vehicle repair major counter current contacting carries out interphase mass transfer.Volatile components in liquid phase enter vapour phase, the difficult volatilization group in vapour phase
Divide and is transferred to liquid phase.Distillate by be high-purity volatile components, tower bottom product by be high-purity difficult volatile component.Feed inlet
Above tower section, the further concentrate of volatile components in upflowing vapor, referred to as rectifying section；Feed inlet tower section below, under
Volatile components, referred to as stripping section are extracted in descending liquid body.The combination of two sections of operations, keeps two components in liquid mixture completeer
It detaches entirely, produces two kinds of products of required purity.Why continuous rectification can be such that liquid mixture is more completely divided
From key is the application to flow back.Reflux includes tower top high concentration volatile components liquid（After cooled）With bottom of tower high concentration
Difficult volatile component steams（It is heated）Both gas returns in tower, and the two vapour-liquid, which flows back, forms the vehicle repair major of counter current contacting, saves
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, then by
Gradually heating vaporization, from after the steam of tower top out is condensed, a part is sent back to as liquid product, another part is distillated as reflux
In tower, after liquid composition drops to specified value in kettle to be heated, by its primary discharge, the distillation operation of next group is then carried out.Cause
This, batch fractionating is compared with continuous rectification, and there are two features for tool：（1）Batch fractionating is transient；（2）Batch fractionating tower
Only rectifying section.
Since the water, light oil and the ester type compound amount that are 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 in order to further illustrate the present invention and technique effect, below to 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（Boiling
The 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
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 glycols, 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
The purity of collection, obtained hexylene glycol is 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, Hydrogenation hexylene glycol is used for as raw material.
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%；Heavy oil（Boiling
The point impurity higher than hexylene glycol）：1.8%；It is based on material composition 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 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
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 glycols, 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
The purity of collection, obtained hexylene glycol is 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, Hydrogenation hexylene glycol is used for as raw material.
Product methanol purity >=99.90% obtained by above example, hexylene glycol purity >=99.80%, it was demonstrated that this work
Artistic skill is enough effectively to detach 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, to reduce energy consumption and cost for the purification of product.
Claims (9)
1. a kind of crude product distillation system of the hexylene glycol Han 1,6-, which is characterized in that include：
The first continuous rectification apparatus, the second continuous rectification apparatus and the third continuous rectification apparatus being connected with each other, and with described the
4th batch rectification device of two continuous rectification apparatus connection, aforementioned each rectifier unit separately include tower body;4th interval
Rectifier unit also includes the heating kettle set on tower body bottom；The tower body bottom temperature of first, second, third continuous rectification apparatus
The boiling point temperature range of the crude product of the hexylene glycol Han 1,6- steps up according to degree；
Feed inlet, the tower body of first continuous rectification apparatus are equipped in the middle part of the side of the tower body of first continuous rectification apparatus
Outlet at bottom connects the feed inlet in the middle part of the tower body side of second continuous rectification apparatus, second continuous rectification apparatus
Tower body outlet at bottom connects the feed inlet in the middle part of the tower body side of the third continuous rectification apparatus；The second continuous rectification dress
The tower body top exit set connects the feed inlet of the heating kettle of the 4th batch rectification device, and second continuous rectification is made to fill
Water, light oil and the ester type compound that the tower body top exit set comes out are added in the heating kettle of the 4th batch rectification device
Hot vapour isolates water and light oil from tower body top, and remaining ester type compound in the heating kettle passes through the discharge of the heating kettle
Mouth is connected to Hydrogenation 1, the reactor or storage tank of 6- hexylene glycols.
2. distillation system according to claim 1, it is characterised in that：The heating kettle is comprising autoclave body and in autoclave body
Heating device, the material that the tower body top exit of second continuous rectification apparatus is isolated are collected into the autoclave body.
3. distillation system according to claim 1 or 2, it is characterised in that：The tower body of first continuous rectification apparatus is
Atmospheric tower, and the feed inlet of the tower body be located at tower body height from bottom to up 10/50 ~ 30/50 position；Temperature at the top of the tower body
Degree is 60-70 DEG C, and the tower body bottom is equipped with tower reactor, and bottom temperature is 80-180 DEG C.
4. distillation system according to claim 3, it is characterised in that：The tower body of second continuous rectification apparatus is decompression
Tower, the feed inlet of the tower body be located at tower body height from bottom to up 15/50 ~ 30/50 position；The third continuous rectification dress
The tower body set is vacuum tower, the feed inlet of the tower body be located at tower body height from bottom to up 15/50 ~ 35/50 position；It is described
The tower body of 4th batch rectification device is vacuum tower, the feed inlet tower body height of the tower body from bottom to up 10/50 ~ 30/50
Position.
5. one kind is by dimethyl adipate Hydrogenation 1, the crude product rectificating method of 6- hexylene glycols, in dimethyl adipate Hydrogenation
After the completion of 1,6- hexylene glycol reaction step, product is to include methanol, water, light oil, ester type compound, 1,6- hexylene glycols and heavy oil
Thick hexylene glycol mixture；It is characterized in that：
The method includes two stages of continuous rectification and batch fractionating, the continuous rectification stage includes first be connected with each other
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 is fed in the middle part of the tower body of second continuous rectification apparatus, is continuously isolated 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, hexylene glycol is continuously isolated 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 is discharged；
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 Hydrogenation 1 as raw material, the reaction step of 6- hexylene glycols recycles.
6. rectificating method according to claim 5, it is characterised in that：The tower body of first continuous rectification apparatus is normal pressure
Tower, and the feed inlet of the tower body is located at the position of tower body height 10/50-30/50 from bottom to up；The tower body head temperature is
60-70 DEG C, the tower body bottom is equipped with tower reactor, and bottom temperature is 80-180 DEG C.
7. rectificating method according to claim 6, it is characterised in that：The feed inlet of the tower body be located at tower body height from
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 is 120-220 DEG C, and the vacuum degree inside the tower body is absolute pressure≤50KPa.
8. rectificating method according to claim 7, it is characterised in that：The tower body of the third continuous rectification apparatus is decompression
Tower, the feed inlet of the tower body be located at tower body height from bottom to up 15/50 ~ 35/50 position；The tower body head temperature is
120-220 DEG C, the tower body bottom is equipped with tower reactor, and bottom temperature is 150-240 DEG C, and the vacuum degree inside the tower body is absolute pressure
≤20KPa。
9. rectificating method according to claim 8, it is characterised in that：The tower body of 4th batch rectification device is decompression
Tower, the feed inlet of the tower body be located at tower body height from bottom to up 10/50 ~ 30/50 position；The tower body head temperature is
0-100 DEG C, the heating temperature in the kettle is 120-220 DEG C, and the vacuum degree inside the tower body is absolute pressure≤50KPa.
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| CN109438412A (en) * | 2018-11-14 | 2019-03-08 | 大晶信息化学品（徐州）有限公司 | A kind of method of purification of crude product dioxane |
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