CN106117013A - The method of purification of a kind of 1,3 propylene glycol and device thereof - Google Patents
The method of purification of a kind of 1,3 propylene glycol and device thereof Download PDFInfo
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- CN106117013A CN106117013A CN201610539547.8A CN201610539547A CN106117013A CN 106117013 A CN106117013 A CN 106117013A CN 201610539547 A CN201610539547 A CN 201610539547A CN 106117013 A CN106117013 A CN 106117013A
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- rectifying column
- tower
- filler
- column
- side take
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention provides a kind of 1, the method of purification of 3 propylene glycol, comprise the following steps: 1 will obtained through biosynthesis, the 3 thick products of propylene glycol are added sequentially to the first rectifying column and Second distillation column carries out rectification under vacuum, to remove water and 2 successively, 3 butanediols, then the tower bottoms in Second distillation column is joined the 3rd rectifying column and carry out rectification under vacuum, side take-off 1 in the 3rd rectifying column, 3 propylene glycol.The method of purification that the present invention provides, is operated by fine vacuum continuous rectification and side take-off high purity product, can improve product purity and product yield, and save equipment investment.Present invention also offers a kind of 1, the purifying plant of 3 propylene glycol, the Second distillation column connected including the first rectifying column and the first rectifying column and the 3rd rectifying column being connected with Second distillation column, 3rd rectifying column is provided with 1,3 propylene glycol collection devices, being additionally provided with side take-off mouth on 3rd rectifying column, 1,3 propylene glycol collection device is connected with side take-off mouth.The apparatus structure that the present invention provides is simple.
Description
Technical field
The present invention relates to, in field of chemical engineering, be specifically related to method of purification and the device thereof of a kind of 1,3-PD.
Background technology
1,3-PD (1,3-propanediol, be abbreviated as 1,3-PDO) is a kind of important industrial chemicals, both can use
In the synthesis of multi-medicament, polyester, medicine intermediate and novel antioxidant, simultaneously can also be as antifreeze and solvent.1,3-
Propylene glycol is also the important monomer of synthesizing new thermoplastic polyester product, the polyester especially synthesized with 1,3-PD for monomer
Material poly terephthalic acid diol ester (PTT), because having good elasticity, stain resistance, good coloring and good life
Thing degradability etc. receives more and more attention, and the market space is huge, and also the large-scale production for 1,3-PD illustrates U.S.
Good prospect, so that the research and development of 1,3-PD are increasingly subject to people's attention.
At present, 1,3-PD has realized the method for industrialized production two kinds, and a kind of is the acrylic aldehyde of Degussa company
Hydration hydrogenization method, another kind is the oxirane hydroformylation method of Shell company.Wherein, acrolein hydration hydrogenization method is with propylene
Aldehyde is raw material, is hydrated and obtains 3-HPA under acidic catalyst effect, then utilizes hydrogenation catalyst by 3-hydroxyl
Propionic aldehyde hydrogenation prepares 1,3-propylene glycol.Oxirane hydroformylation method uses oxirane, CO and H2For raw material, make at catalyst
Generate 3-HPA with lower by hydroformylation reaction, prepare 1 through catalytic hydrogenation again after separating-purifying 3-HPA, 3-third
Glycol；The method can also be hydrogenated with intermediate product 3-HPA by direct in-situ, and a step obtains 1,3-PD.
But above two method broadly falls into chemical synthesis, exist many not enough.Such as, the one-tenth of acrolein hydration hydrogenization method
This is the highest, and its raw material propylene aldehyde is a kind of severe toxicity, inflammable, explosive chemicals, does not meets the requirement of Green Chemistry.Oxirane
Although hydroformylation method production cost is relatively low, technology maturation, but its equipment investment is big, and the preparation technology of catalyst is complex.
Along with application and the demand of composite fibre materials PTT constantly expand, the existing yield of 1,3-PD can not meet market need
Asking, its production method is also needed improvement badly and updates.
Produce 1,3-propylene glycol for raw material by microbe transformation method with glycerol and there is positive realistic meaning.Along with development
Increasing substantially of Chinese Home vegetable oil yield and using in a large number in chemical industry, glycerol is in world markets by progressively surplus also
And prices, make exploitation biotechnology be become by the product (such as 1,3-PD) that glycerol is converted into high price as substrate
For the focus attracted attention.
The reacted mixture of glycerol biosynthesis mainly contains 1,3-propylene glycol, 2,3-butanediol, water, glycerol, acid
(lactic acid, succinic acid etc.), cell debris and enzyme etc..Want the high-purity 1,3-PD goal object obtaining utilizing,
Needing to carry out mixture a series of process, most important of which one ring is exactly product purification.Product purification is typically adopted at present
With rectification method, but the product purity that the method for rectification at present obtains is the highest, product yield is the highest, and equipment investment is relatively big, because of
This, it is necessary to a kind of method that new purifying 1,3-propylene glycol is provided.
Summary of the invention
For solving the problems referred to above, the invention provides the method for purification of a kind of 1,3-PD, this method of purification is simple, have
Effect, the 1,3-PD purity obtained is higher, and yield is preferable, present invention also offers the purifying plant of a kind of 1,3-PD.
First aspect present invention provides the method for purification of a kind of 1,3-PD, comprises the following steps:
The thick product of 1,3-propylene glycol obtained through biosynthesis is added sequentially to the first rectifying column and Second distillation column enters
Row rectification under vacuum, to remove water and 2,3-butanediol successively, then joins the 3rd by the tower bottoms in described Second distillation column
Rectifying column carries out rectification under vacuum, side take-off 1,3-PD in described 3rd rectifying column.
Wherein, the number of plates that described side take-off 1,3-PD position is corresponding is positioned at described 3rd rectifying column theoretical tray
At the 1/5-1/4 of number.
Wherein, described 3rd rectifying column is provided with oil sump tank, described oil sump tank is additionally provided with extraction bucket, described 1,3-the third two
Alcohol is extracted out outside tower, with 1,3-PD described in side take-off through described bucket of extracting out after being collected by described oil sump tank.
Wherein, described 3rd rectifying column from tower top to tower reactor include successively first paragraph filler, second segment filler, the 3rd section fill out
Material and the 4th section of filler, described oil sump tank is between described first paragraph filler and second segment filler.
Wherein, the material that described 3rd rectifying column tower top obtains is joined continuation rectification in Second distillation column.
Operation wherein, in purification process, in described first rectifying column, described Second distillation column and described 3rd rectifying column
Pressure is respectively 80-100mmHg, 10-20mmHg, 5-10mmHg.
The method of purification of the 1,3-PD that first aspect present invention provides, is operated and side by fine vacuum continuous rectification
Line extraction high purity product, can improve product purity, improves product yield, and saves equipment investment.The 1,3-third obtained
The purity of glycol is not less than 99.8%, and the yield of 1,3-PD is not less than 95%.It addition, the present invention that purity is also obtained is higher
2,3-butanediol and glycerol.
Second aspect present invention provides the purifying plant of a kind of 1,3-PD, including the first rectifying column and described
Second distillation column that one rectifying column connects and the 3rd rectifying column that is connected with described Second distillation column, described first rectifying column is used
In removing the water in the thick product of 1,3-PD that biosynthesis obtains, described Second distillation column is for removing through biosynthesis
2,3-butanediol in the thick product of 1,3-PD obtained, is provided with 1,3-PD collection device in described 3rd rectifying column,
Being additionally provided with side take-off mouth on described 3rd rectifying column, described 1,3-PD collection device is connected with described side take-off mouth.
Wherein, the number of plates that described 1,3-PD collection device is corresponding is positioned at described 3rd theoretical number of plates of rectifying tower
At 1/5-1/4.
Wherein, described 1,3-PD collection device is oil sump tank, is provided with extraction bucket, described oil sump tank in described oil sump tank
After the 1,3-PD collected is drawn to described side take-off mouth by described extraction bucket and then be drawn out of outside tower, adopt with side line
Go out described 1,3-propylene glycol.
Wherein, the tower top of described 3rd rectifying column is connected by pipeline with described Second distillation column, for by the described 3rd
The material that rectifying column tower top obtains joins continuation rectification in Second distillation column.
The purifying plant of the 1,3-PD that second aspect present invention provides, apparatus structure is simple, uses this device to obtain
1,3-PD purity higher, yield is the highest.
To sum up, beneficial effect of the present invention includes the following aspects:
1, the method for purification of the 1,3-PD that the present invention provides, is operated and side take-off by fine vacuum continuous rectification
High purity product, can improve product purity, improves product yield, and saves equipment investment；
2, the purifying plant of 1,3-PD that the present invention provides, apparatus structure is simple, use that this device obtains 1,3-
Propylene glycol purity is higher, and yield is the highest.
Accompanying drawing explanation
The purification process schematic diagram of the 1,3-propylene glycol that Fig. 1 provides for an embodiment of the present invention；
The purification process schematic diagram of the 1,3-propylene glycol that Fig. 2 provides for another embodiment of the present invention.
Detailed description of the invention
The following stated is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications are also considered as
Protection scope of the present invention.
Purification process schematic diagram with reference to the 1,3-PD that Fig. 1, Fig. 1 provide for an embodiment of the present invention；The present invention
First aspect provides the method for purification of a kind of 1,3-PD, comprises the following steps:
The thick product of 1,3-propylene glycol obtained through biosynthesis is added sequentially to the first rectifying column 1 and Second distillation column 2
Carry out rectification under vacuum, to remove water and 2,3-butanediol successively, then the tower bottoms in Second distillation column 2 is joined the 3rd essence
Evaporate tower 3 and carry out rectification under vacuum, side take-off 1,3-PD in the 3rd rectifying column 3.
The reacted mixture of glycerol biosynthesis mainly contains 1,3-propylene glycol, 2,3-butanediol, water, glycerol, acid
(lactic acid, succinic acid etc.), cell debris and enzyme etc., mixture obtains (such as membrane filtration, activated carbon adsorption) after pretreatment
To the thick product of 1,3-PD, the thick product of 1,3-PD includes 1,3-PD, 2,3-butanediol, water, glycerol, acid (breast
Acid, succinic acid etc.), the content of acid is the least, also other unknown impurities of trace.Follow-up by the employing of thick for 1,3-propylene glycol product
The method of purification of the 1,3-propylene glycol that the present invention provides purifies.
In an embodiment of the present invention, thick for the 1,3-PD obtained through biosynthesis product is joined the first rectifying column
After carrying out rectification under vacuum, the water more than 99.9% is from removed overhead, and the material that tower reactor obtains enters the second rectification after pump supercharging
Tower proceeds rectification under vacuum, and tower top goes out 2,3-butanediol, and the material that tower reactor obtains enters the 3rd rectifying column after pump supercharging and enters
Row rectification under vacuum, the side take-off 1,3-PD in the 3rd rectifying column, tower top goes out a small amount of light component materials, and tower reactor is discharged
Glycerol.
In an embodiment of the present invention, in purification process, the operation pressure of the first rectifying column is 80-100mmHg.
Here operation pressure refers to the pressure of tower top.
Owing to the boiling point of glycerol is higher, normal pressure is issued to 297 DEG C, and glycerol has the risk of polymerization when temperature is higher,
Cause the blockage problem of tower reactor, reboiler and outlet conduit.In order to avoid blocking, cause being interrupted of operation and dangerous sending out
Raw, rectifying column of the present invention all uses fine vacuum to operate.
As it is shown in figure 1, in an embodiment of the present invention, the first rectifying column built-in raising effect separating filler, the first rectifying column
Four sections of fillers, the respectively first filler the 11, second filler the 12, the 3rd filler 13 and the 4th filler is included successively from tower top to tower reactor
14。
In an embodiment of the present invention, in the first rectifying column, every section of filler is arranged over liquid distribution trough.
Every section of filler is arranged over liquid distribution trough, for uniformly being divided by the liquid that charging or epimere filler are collected
Cloth, makes filler play high efficiency to greatest extent, and this structure space occupy-place is low, has good distributed effect, anti-carry secretly and press
Drop relatively low.
In an embodiment of the present invention, between every section of filler, be provided with anti-wall flow circle, anti-wall flow circle weld with tower wall and with
Described tower wall becomes 75 ° of angles.
The position between liquid distribution trough in the present invention one preferred implementation, above every section of filler and next section of filler
Install anti-wall flow circle, it may be assumed that the liquid distribution trough above every section of filler is respectively designated as first liquid distributor, second liquid
Distributor, the 3rd liquid distribution trough and the 4th liquid distribution trough, between the first filler and second liquid distributor, the second filler
With the 3rd be designed with anti-wall flow circle between liquid distribution trough and between the 3rd filler and the 4th liquid distribution trough.
Due to the characteristic of structured packing, along with liquid flows from top to bottom from filler, liquid has a kind of from trend tower wall collection
Poly-trend, this is disadvantageous for the separating-purifying of 1,3-PD, and the present invention is in every section of filler and liquid distribution
Between device, an anti-wall flow circle can be set, the liquid of tower wall is collected and is directed on the collecting board of next section of filler distribution device.Anti-
Wall stream circle is a circulus, welds with tower wall, becomes 75 ° of angles with tower wall, forms a downward opening pyramidal structure.
In an embodiment of the present invention, condenser that the first rectifying column also includes being connected with the first rectifying column, return tank, pump
And reboiler.The connected mode of the equipment such as condenser and the first rectifying column is that industry routine selects, and is not specially limited at this.
In an embodiment of the present invention, the first rectifying column being additionally provided with tower reactor reboiler return port, tower reactor reboiler returns
It is provided with gas distributor between mouth and the 4th filler, is distributed for the gas phase that described reboiler is returned.3rd rectifying column
It is provided with tower reactor reboiler return port, for high-purity separation, above tower reactor reboiler return port and below the 4th filler,
Being provided with a gas distributor, gas distributor can carry out pre-distribution to the gas phase that reboiler returns, and improves the effect of filler
Rate.
The structure of gas distributor is not done particular determination by the present invention, selects for industry routine.
In an embodiment of the present invention, in purification process, the operation pressure of Second distillation column is 10-20mmHg.
As it is shown in figure 1, in an embodiment of the present invention, Second distillation column built-in raising effect separating filler, Second distillation column
Four sections of fillers, respectively the Ith section filler 21, the IIth section of filler 22, the IIIth section of filler 23 and is included successively from tower top to tower reactor
IV section of filler 24.
In an embodiment of the present invention, in Second distillation column, every section of filler is arranged over liquid distribution trough.
Every section of filler is arranged over liquid distribution trough, for uniformly being divided by the liquid that charging or epimere filler are collected
Cloth, makes filler play high efficiency to greatest extent, and this structure space occupy-place is low, has good distributed effect, anti-carry secretly and press
Drop relatively low.
In an embodiment of the present invention, between every section of filler, be provided with anti-wall flow circle, anti-wall flow circle weld with tower wall and with
Described tower wall becomes 75 ° of angles.
The position between liquid distribution trough in the present invention one preferred implementation, above every section of filler and next section of filler
Install anti-wall flow circle, it may be assumed that the liquid distribution trough above every section of filler is respectively designated as first liquid distributor, second liquid
Distributor, the 3rd liquid distribution trough and the 4th liquid distribution trough, at the Ith section between filler and second liquid distributor, the IIth section
Between filler and the 3rd liquid distribution trough and the IIIth section be designed with anti-wall flow circle between filler and the 4th liquid distribution trough.
Due to the characteristic of structured packing, along with liquid flows from top to bottom from filler, liquid has a kind of from trend tower wall collection
Poly-trend, this is disadvantageous for the separating-purifying of 1,3-PD, and the present invention is in every section of filler and liquid distribution
Between device, an anti-wall flow circle can be set, the liquid of tower wall is collected and is directed on the collecting board of next section of filler distribution device.Anti-
Wall stream circle is a circulus, welds with tower wall, becomes 75 ° of angles with tower wall, forms a downward opening pyramidal structure.
In an embodiment of the present invention, condenser that Second distillation column also includes being connected with Second distillation column, return tank, pump
And reboiler.The equipment such as condenser are that industry routine selects with the connected mode of Second distillation column, are not specially limited at this.
In an embodiment of the present invention, Second distillation column being additionally provided with tower reactor reboiler return port, tower reactor reboiler returns
It is provided with gas distributor between mouth and the IVth section of filler, is distributed for the gas phase that described reboiler is returned.Second rectification
Tower is provided with tower reactor reboiler return port, for high-purity separation, with the IVth section of filler above tower reactor reboiler return port
Lower section, is provided with a gas distributor, and gas distributor can carry out pre-distribution to the gas phase that reboiler returns, and improves filler
Efficiency.
The structure of gas distributor is not done particular determination by the present invention, selects for industry routine.
In an embodiment of the present invention, in purification process, the operation pressure of the 3rd rectifying column is 5-10mmHg.
The present invention uses the mode extraction 1,3-PD of side take-off, makes the light composition impurity of 1,3-PD and some divide
Leaving, the product purity obtained is higher, and impurity is less, and yield is higher.Even if when charging containing boiling point between 2,3-fourth two
During component between alcohol and 1,3-PD, the purity of purpose product 1,3-PD is the highest.
In an embodiment of the present invention, the number of plates corresponding to side take-off 1,3-PD position is positioned at the 3rd rectifying column reason
At the 1/5-1/4 of the opinion number of plates.Rectifying column has certain theoretical cam curve, the tower that side take-off 1,3-PD position is corresponding
Plate numerical digit is at the 1/5-1/4 of the 3rd theoretical number of plates of rectifying tower, and the 1,3-PD obtained at this position side take-off is pure
Spend higher.
In an embodiment of the present invention, the position of oil sump tank is corresponding with the position of side take-off mouth.
In an embodiment of the present invention, oil sump tank is used to collect 1,3-PD side take-off 1,3-PD.
As it is shown in figure 1, in an embodiment of the present invention, the 3rd rectifying column is provided with oil sump tank 4, oil sump tank is additionally provided with and takes out
Going out bucket, 1,3-PD is extracted out outside tower through extraction bucket, with side take-off 1,3-PD after being collected by oil sump tank.
As it is shown in figure 1, in an embodiment of the present invention, the tower wall of the 3rd rectifying column is provided with side take-off mouth 5, oil sump tank 4
Being connected with side take-off mouth 5, the 1,3-PD that oil sump tank is collected is drawn to through side take-off mouth by extracting bucket out, and then
It is drawn out of outside tower, with side take-off 1,3-PD.
In an embodiment of the present invention, side take-off mouth is connected by pipeline and a pump, 1 will extracted out in bucket by pump,
Ammediol is drawn to outside tower.
In an embodiment of the present invention, the purifying plant of described 1,3-PD also includes a storage tank, and storage tank is adopted with side line
Outlet connects, for storing the 1,3-PD of side take-off.
In an embodiment of the present invention, the temperature of side take-off mouth is 100 DEG C-109 DEG C.
Side take-off uses oil sump tank design, and the liquid got off from epimere filler liquid collection trough oil sump tank is complete
Entirely collect, then by extracting bucket extraction out, the gas phase that lower floor's filler rises is passed through by air rising hole, is evenly distributed, Er Qieqi
Phase aisle spare is big, and pressure drop is little.Internal reflux part is imported in the distributing slot of lower floor's filler by internal reflux pipe, and liquid uniformly divides
Cloth.
In an embodiment of the present invention, the 3rd rectifying column built-in raising effect separating filler.
In the present invention one preferred implementation, high efficiency separation filler is that metallic plate corrugated regular filler, metal gauze are regular
Filler, metal mesh opening ripple packing, grid packing, Impulse packing or efficiently random packing.
As it is shown in figure 1, in an embodiment of the present invention, the 3rd rectifying column includes first paragraph filler successively from tower top to tower reactor
31, second segment filler 32, the 3rd section of filler 33 and the 4th section of filler 34, oil sump tank 4 is positioned at first paragraph filler 31 and second segment is filled out
Between material 32
In the present invention one preferred implementation, oil sump tank 4 is positioned at first paragraph filler 31 and the interposition of second segment filler 32
Put.
In an embodiment of the present invention, the structure of oil sump tank is that industry routine selects, and does not do particular determination at this, such as may be used
To use beam groove integral type oil sump tank.
In an embodiment of the present invention, every section of filler is arranged over liquid distribution trough.
Every section of filler is arranged over liquid distribution trough, for uniformly being divided by the liquid that charging or epimere filler are collected
Cloth, makes filler play high efficiency to greatest extent, and this structure space occupy-place is low, has good distributed effect, anti-carry secretly and press
Drop relatively low.
In an embodiment of the present invention, between every section of filler, be provided with anti-wall flow circle, anti-wall flow circle weld with tower wall and with
Described tower wall becomes 75 ° of angles.
In an embodiment of the present invention, the position between liquid distribution trough above every section of filler and next section of filler sets
Put anti-wall flow circle, it may be assumed that the liquid distribution trough above every section of filler is respectively designated as first liquid distributor, second liquid distribution
Device, the 3rd liquid distribution trough and the 4th liquid distribution trough, between first paragraph filler and second liquid distributor, second segment filler
And the 3rd between liquid distribution trough and the 3rd section be designed with anti-wall flow circle between filler and the 4th liquid distribution trough.
Due to the characteristic of structured packing, along with liquid flows from top to bottom from filler, liquid has a kind of from trend tower wall collection
Poly-trend, this is disadvantageous for the separating-purifying of 1,3-PD, and the present invention is in every section of filler and liquid distribution
Between device, an anti-wall flow circle can be set, the liquid of tower wall is collected and is directed on the collecting board of next section of filler distribution device.Anti-
Wall stream circle is a circulus, welds with tower wall, becomes 75 ° of angles with tower wall, forms a downward opening pyramidal structure.
The concrete structure of anti-wall flow circle is not done particular determination by the present invention, selects for industry routine.
In an embodiment of the present invention, condenser that the 3rd rectifying column also includes being connected with the 3rd rectifying column, return tank, pump
And reboiler.The connected mode of the equipment such as condenser and the 3rd rectifying column is that industry routine selects, and is not specially limited at this.
In an embodiment of the present invention, the 3rd rectifying column being additionally provided with tower reactor reboiler return port, tower reactor reboiler returns
It is provided with gas distributor between mouth and the 4th section of filler, is distributed for the gas phase that described reboiler is returned.3rd rectification
Tower is provided with tower reactor reboiler return port, for high-purity separation, with the 4th section of filler above tower reactor reboiler return port
Lower section, is provided with a gas distributor, and gas distributor can carry out pre-distribution to the gas phase that reboiler returns, and improves filler
Efficiency.
The structure of gas distributor is not done particular determination by the present invention, selects for industry routine.
For ensureing yield, the logistics that the 3rd rectifying column tower top contains a small amount of light component is circulated back to Second distillation column.If
Containing not clear impurity, the most do not circulate and be expelled directly out outside device, in order to avoid causing impurity to form in intrasystem accumulation.
In an embodiment of the present invention, the material that the 3rd rectifying column tower top obtains is joined Second distillation column continues essence
Evaporate.So can improve the yield of product.
In another embodiment of the present invention, the material that the 3rd rectifying column tower top obtains directly is exported.
The purification process schematic diagram of the 1,3-propylene glycol that Fig. 1 provides for an embodiment of the present invention；With reference to Fig. 1, the present invention
In embodiment, the 1,3-PD thick product S1 obtained through biosynthesis enters the first rectifying column 1 by the first charging aperture and enters
Row rectification under vacuum, the water vapour obtained at tower top, after condenser condenses, produces condensed fluid, and condensed fluid enters in return tank
After, part enters the first rectifying column as backflow and continues rectification, and remainder S2 (water) exports.The tower bottoms of part is by again
Obtain gas phase after boiling device intensification gasification and enter continuation rectification in the first rectifying column.Another part tower bottoms S3 is pressurizeed by pump P1
Rear formation liquid S4, S4 enter in Second distillation column 2 by the second charging aperture, and the 2,3-butanediol obtained at tower top passes through condensation
After device condensation, producing condensed fluid, after condensed fluid enters in return tank, part enters Second distillation column as backflow and continues essence
Evaporating, remainder S5 (2,3-butanediol) directly exports.The tower bottoms of part enters by obtaining gas phase after reboiler intensification gasification
Enter continuation rectification in Second distillation column.Another part tower bottoms S6 is formed after pump P2 supercharging liquid S7, S7 enter by the 3rd
Material mouth enters the 3rd rectifying column 3 and carries out rectification under vacuum, and side take-off 1,3-PD S9 in the 3rd rectifying column, tower top obtains
Light component materials, after condenser condenses, produces condensed fluid, and after condensed fluid enters in return tank, part enters as backflow
3rd rectifying column continues rectification, and remainder S8 directly exports.The glycerol part that tower reactor obtains is heated up by reboiler and gasifies
After obtain gas phase and enter the 3rd rectifying column continues rectification, another part glycerol S10 is directly exported.
In an embodiment of the present invention, the first charging aperture is positioned at the first filler 11 of the first rectifying column and the second filler 12
Centre position.
In an embodiment of the present invention, the second charging aperture is positioned at the IIth section of filler 22 of Second distillation column and the IIIth section of filler
The centre position of 23.
In an embodiment of the present invention, the 3rd charging aperture is positioned at the second segment filler 32 of the 3rd rectifying column and the 3rd section of filler
The centre position of 33.
The purification process schematic diagram of the 1,3-propylene glycol that Fig. 2 provides for another embodiment of the present invention.As in figure 2 it is shown, the
One rectifying column is identical with above-mentioned with the purification process of Second distillation column, and difference is: it is light that the 3rd rectifying column tower top obtains
Component materials, after condenser condenses, produces condensed fluid, and after condensed fluid enters in return tank, part enters the as backflow
Three rectifying columns 3 continue rectification, and remainder S8 input continues rectification to Second distillation column 2.
The method of purification of the 1,3-PD that first aspect present invention provides, is operated and side by fine vacuum continuous rectification
Line extraction high purity product, can improve the pure and mild product yield of product, and save equipment investment, shortens the rectification time, reduces
Energy consumption.The purity of the 1,3-PD obtained is not less than 99.8%, can be used for subsequent polymerisation reaction, and the yield of 1,3-PD is not
Less than 95%.It addition, the purity of 2,3-butanediol of the present invention is about 99.6%, the purity of glycerol is about 95%.Therefore, originally
Invention is also obtained the higher 2,3-butanediol of purity and glycerol.
Seeing figures.1.and.2, second aspect present invention provides the purifying plant of a kind of 1,3-PD, including the first essence
Evaporate the Second distillation column 2 that tower 1 is connected and the 3rd rectifying column 3 being connected with Second distillation column 2, the first essence with the first rectifying column 1
Evaporating tower 1 for removing water in the thick product of 1,3-PD that biosynthesis obtains, Second distillation column 2 is for removing through biology
2,3-butanediol in the thick product of 1,3-PD that synthesis obtains, is provided with 1,3-PD collection device in the 3rd rectifying column 3
4, the 3rd rectifying column 3 is additionally provided with side take-off mouth 5,1,3-PD collection device 4 is connected with side take-off mouth 5.
In an embodiment of the present invention, the number of plates corresponding to side take-off 1,3-PD position is positioned at the 3rd rectifying column reason
At the 1/5-1/4 of the opinion number of plates.
In an embodiment of the present invention, 1,3-PD collection device is oil sump tank, is provided with extraction bucket, oil-collecting in oil sump tank
The 1,3-PD that case is collected by extract out bucket be drawn to side take-off mouth after so that be drawn out of outside tower, with side take-off 1,3-
Propylene glycol.
In an embodiment of the present invention, being provided with extraction bucket in oil sump tank, the 1,3-PD that oil sump tank is collected is by taking out
After going out bucket extraction, it is drawn out of outside tower after side take-off mouth, with side take-off 1,3-PD.
In an embodiment of the present invention, the position of oil sump tank is corresponding with the position of side take-off mouth.
In an embodiment of the present invention, the 3rd rectifying column includes four sections of fillers successively from tower top to tower reactor, and oil sump tank is positioned at
Between first paragraph filler and second segment filler.
In the present invention one preferred implementation, oil sump tank is positioned at first paragraph filler and the centre position of second segment filler.
In an embodiment of the present invention, the tower top of the 3rd rectifying column is connected with Second distillation column by pipeline, is used for the
The material that three rectifying column tower tops obtain joins continuation rectification in Second distillation column.
If without unknown impurity in the overhead stream of the 3rd rectifying column, then this material can be joined Second distillation column
As circulation logistics to improve yield.If containing unknown impurity in the overhead stream of the 3rd rectifying column, then by straight for this logistics
Run in, do not circulate, in order to avoid impurity is accumulated in tower.Therefore, assembly of the invention can be with flexible Application.
The purifying plant of the 1,3-PD that second aspect present invention provides, apparatus structure is simple, and equipment investment is little, uses
The 1,3-PD purity that this device obtains is higher, and yield is the highest.
Embodiment 1
The method of purification of a kind of 1,3-PD, comprises the following steps:
(1) by the first charging aperture, the 1,3-propylene glycol thick product S1 obtained through biosynthesis is entered the first rectifying column to enter
Row rectification under vacuum, operation pressure is 90mmHg, and the water vapour obtained at tower top, after condenser condenses, produces condensed fluid, cold
After lime set enters in return tank, part enters the first rectifying column as backflow and continues rectification, and remainder S2 exports.Part
Tower bottoms enters continuation rectification in the first rectifying column by obtaining gas phase after reboiler intensification gasification.
(2) enter in Second distillation column by the second charging aperture after another part tower bottoms S3 being pressurizeed by pump, operation
Pressure is 15mmHg, and the 2,3-butanediol obtained at tower top, after condenser condenses, produces condensed fluid, and condensed fluid enters backflow
After in tank, part enters Second distillation column as backflow and continues rectification, and remainder S5 directly exports.The tower bottoms of part leads to
Obtain gas phase after crossing reboiler intensification gasification and enter continuation rectification in Second distillation column.
(3) another part tower bottoms S6 is entered the 3rd rectifying column by the 3rd charging aperture after pump supercharging and carry out decompression essence
Evaporating, side take-off 1,3-PD S9 in the 3rd rectifying column, operation pressure is 5mmHg, and side take-off temperature is 100.3 DEG C,
The position of side take-off is positioned at second segment filler and the centre position of the 3rd section of filler, and the light component materials that tower top obtains is through supercool
After condenser condensation, producing condensed fluid, after condensed fluid enters in return tank, part enters the 3rd rectifying column as backflow and continues essence
Evaporating, remainder S8 directly exports.The glycerol part that tower reactor obtains is heated up by reboiler and obtains gas phase after gasification and enter the
Three rectifying columns continue rectification, another part glycerol S10 is directly exported.
Embodiment 2
The method of purification of a kind of 1,3-PD, comprises the following steps:
Step (1) and step (2) are with embodiment 1；
(3) another part tower bottoms S6 is entered the 3rd rectifying column by the 3rd charging aperture after pump supercharging and carry out decompression essence
Evaporating, the side take-off 1,3-PD S9 in the 3rd rectifying column, the operation pressure of the 3rd rectifying column is 5mmHg, side take-off
Temperature is 100.3 DEG C, and the position of side take-off is positioned at second segment filler and the centre position of the 3rd section of filler, and it is light that tower top obtains
Component materials, after condenser condenses, produces condensed fluid, and after condensed fluid enters in return tank, part enters the as backflow
Three rectifying columns continue rectification, and remainder S8 input continues rectification to Second distillation column.The glycerol part that tower reactor obtains is passed through
Reboiler heats up and obtains after gasifying continuing rectification in gas phase entrance the 3rd rectifying column, is directly exported by another part glycerol S10.
Embodiment 3
The method of purification of a kind of 1,3-PD, comprises the following steps:
(1) by the first charging aperture, the 1,3-propylene glycol thick product S1 obtained through biosynthesis is entered the first rectifying column to enter
Row rectification under vacuum, the operation pressure of the first rectifying column is 80mmHg, and the water vapour obtained at tower top, after condenser condenses, produces
Raw food lime set, after condensed fluid enters in return tank, part enters the first rectifying column as backflow and continues rectification, remainder S2
Output.The tower bottoms of part enters continuation rectification in the first rectifying column by obtaining gas phase after reboiler intensification gasification.
(2) enter in Second distillation column by the second charging aperture after another part tower bottoms S3 being pressurizeed by pump, second
The operation pressure of rectifying column is 10mmHg, and the 2,3-butanediol obtained at tower top, after condenser condenses, produces condensed fluid, cold
After lime set enters in return tank, part enters Second distillation column as backflow and continues rectification, and remainder S5 directly exports.Portion
The tower bottoms divided is heated up by reboiler after gasifying and obtains continuation rectification in gas phase entrance Second distillation column.
(3) another part tower bottoms S6 is entered the 3rd rectifying column by the 3rd charging aperture after pump supercharging and carry out decompression essence
Evaporating, side take-off 1,3-PD S9 in the 3rd rectifying column, the operation pressure of the 3rd rectifying column is 10mmHg, side take-off temperature
Degree is 109.0 DEG C, and the position of side take-off is positioned at second segment filler and the centre position of the 3rd section of filler, obtain light group of tower top
Dividing material after condenser condenses, produce condensed fluid, after condensed fluid enters in return tank, part is as backflow entrance the 3rd
Rectifying column continues rectification, and remainder S8 directly exports.The glycerol part that tower reactor obtains is heated up by reboiler after gasifying and obtains
Enter to gas phase and the 3rd rectifying column continues rectification, another part glycerol S10 is directly exported.
Embodiment 4
The method of purification of a kind of 1,3-PD, comprises the following steps:
(1) by the first charging aperture, the 1,3-propylene glycol thick product S1 obtained through biosynthesis is entered the first rectifying column to enter
Row rectification under vacuum, the operation pressure of the first rectifying column is 100mmHg, the water vapour obtained at tower top after condenser condenses,
Producing condensed fluid, after condensed fluid enters in return tank, part enters the first rectifying column as backflow and continues rectification, remainder
S2 exports.The tower bottoms of part enters continuation rectification in the first rectifying column by obtaining gas phase after reboiler intensification gasification.
(2) enter in Second distillation column by the second charging aperture after another part tower bottoms S3 being pressurizeed by pump, second
The operation pressure of rectifying column is 20mmHg, and the 2,3-butanediol obtained at tower top, after condenser condenses, produces condensed fluid, cold
After lime set enters in return tank, part enters Second distillation column as backflow and continues rectification, and remainder S5 directly exports.Portion
The tower bottoms divided is heated up by reboiler after gasifying and obtains continuation rectification in gas phase entrance Second distillation column.
(3) another part tower bottoms S6 is entered the 3rd rectifying column by the 3rd charging aperture after pump supercharging and carry out decompression essence
Evaporating, side take-off 1,3-PD S9 in the 3rd rectifying column, the tower top pressure of the 3rd rectifying column is 8mmHg, side take-off temperature
Degree is 106.0 DEG C, and the position of side take-off is positioned at second segment filler and the centre position of the 3rd section of filler, obtain light group of tower top
Dividing material after condenser condenses, produce condensed fluid, after condensed fluid enters in return tank, part is as backflow entrance the 3rd
Rectifying column continues rectification, and remainder S8 directly exports.The glycerol part that tower reactor obtains is heated up by reboiler after gasifying and obtains
Enter to gas phase and the 3rd rectifying column continues rectification, another part glycerol S10 is directly exported.
The 1,3-PD purity that the method for purification of the 1,3-PD that the present invention provides obtains is not less than 99.8%, 1,3-
The yield of propylene glycol is not less than 95%.Compare with existing 1,3-PD method of purification, the 1,3-PD that the present invention obtains
Purity higher, yield is higher, illustrates that the method for purification refining effect of the 1,3-PD that the present invention provides is more preferable.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the method for purification of a 1,3-PD, it is characterised in that comprise the following steps:
It is added sequentially in the first rectifying column and Second distillation column carry out by the thick product of 1,3-propylene glycol obtained through biosynthesis
Rectification under vacuum, to remove water and 2,3-butanediol successively, then joins the 3rd essence by the tower bottoms in described Second distillation column
Evaporate and tower carries out rectification under vacuum, side take-off 1,3-PD in described 3rd rectifying column.
2. the method for purification of 1,3-PD as claimed in claim 1, it is characterised in that described side take-off 1,3-PD
The number of plates corresponding to position is positioned at the 1/5-1/4 of described 3rd theoretical number of plates of rectifying tower.
3. the method for purification of 1,3-PD as claimed in claim 2, it is characterised in that be provided with collection in described 3rd rectifying column
Fuel tank, is additionally provided with extraction bucket in described oil sump tank, described 1,3-PD is taken out through described extraction bucket after being collected by described oil sump tank
Go out outside tower, with 1,3-PD described in side take-off.
4. the method for purification of 1,3-PD as claimed in claim 3, it is characterised in that described 3rd rectifying column from tower top to
Tower reactor includes first paragraph filler, second segment filler, the 3rd section of filler and the 4th section of filler successively, and described oil sump tank is positioned at described
Between one section of filler and described second segment filler.
5. the method for purification of 1,3-PD as claimed in claim 1, it is characterised in that described 3rd rectifying column tower top is obtained
To material join in described Second distillation column continuation rectification.
6. the method for purification of 1,3-PD as claimed in claim 1, it is characterised in that in purification process, described first essence
The operation pressure evaporated in tower, described Second distillation column and described 3rd rectifying column is respectively 80-100mmHg, 10-20mmHg, 5-
10mmHg。
7. the purifying plant of a 1,3-PD, it is characterised in that include that the first rectifying column is connected with described first rectifying column
Second distillation column and the 3rd rectifying column that is connected with described Second distillation column, described first rectifying column is for removing through biology
Water in the thick product of 1,3-PD that synthesis obtains, described Second distillation column is for removing 1 obtained through biosynthesis, 3-third
2,3-butanediol in the thick product of glycol, is provided with 1,3-PD collection device, described 3rd rectification in described 3rd rectifying column
Being additionally provided with side take-off mouth on tower, described 1,3-PD collection device is connected with described side take-off mouth.
8. the purifying plant of 1,3-PD as claimed in claim 7, it is characterised in that described 1,3-PD collection device
The corresponding number of plates is positioned at the 1/5-1/4 of described 3rd theoretical number of plates of rectifying tower.
9. the purifying plant of 1,3-PD as claimed in claim 8, it is characterised in that described 1,3-PD collection device
For oil sump tank, being provided with extraction bucket in described oil sump tank, the 1,3-PD that described oil sump tank is collected is taken out by described extraction bucket
Go out to described side take-off mouth and then be drawn out of outside tower, with 1,3-PD described in side take-off.
10. the purifying plant of 1,3-PD as claimed in claim 7, it is characterised in that the tower top of described 3rd rectifying column
It is connected by pipeline with described Second distillation column, for the material that described 3rd rectifying column tower top obtains is joined the second rectification
Tower continues rectification.
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| CN201610539547.8A CN106117013A (en) | 2016-07-08 | 2016-07-08 | The method of purification of a kind of 1,3 propylene glycol and device thereof |
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| CN201610539547.8A CN106117013A (en) | 2016-07-08 | 2016-07-08 | The method of purification of a kind of 1,3 propylene glycol and device thereof |
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| CN108654129A (en) * | 2018-06-05 | 2018-10-16 | 云南国润香料制造有限公司 | A kind of the eucalyptus oil rectifier unit and processing method of Fractional Collections rectifying liquid |
| CN110354650A (en) * | 2019-07-30 | 2019-10-22 | 云南雷允上理想药业有限公司 | A kind of vacuum system dehumidifying unit |
| CN110818900A (en) * | 2019-12-12 | 2020-02-21 | 浙江润禾有机硅新材料有限公司 | Method and production system for continuously catalyzing, synthesizing and separating high-purity low-viscosity dimethyl silicone oil |
| WO2021198563A1 (en) * | 2020-04-03 | 2021-10-07 | Upm-Kymmene Corporation | Recovering mono-propylene glycol |
| CN115400706A (en) * | 2022-08-29 | 2022-11-29 | 山东海科新源材料科技股份有限公司 | Device and method for purifying and deodorizing cosmetics grade 1,3-butanediol |
| CN115636730A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | Method for purifying and decoloring 1, 3-propylene glycol crude product |
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| CN108654129A (en) * | 2018-06-05 | 2018-10-16 | 云南国润香料制造有限公司 | A kind of the eucalyptus oil rectifier unit and processing method of Fractional Collections rectifying liquid |
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| CN110818900B (en) * | 2019-12-12 | 2021-10-22 | 浙江润禾有机硅新材料有限公司 | Method and production system for continuously catalyzing, synthesizing and separating high-purity low-viscosity dimethyl silicone oil |
| WO2021198563A1 (en) * | 2020-04-03 | 2021-10-07 | Upm-Kymmene Corporation | Recovering mono-propylene glycol |
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| CN115636730A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | Method for purifying and decoloring 1, 3-propylene glycol crude product |
| CN115400706A (en) * | 2022-08-29 | 2022-11-29 | 山东海科新源材料科技股份有限公司 | Device and method for purifying and deodorizing cosmetics grade 1,3-butanediol |
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