CN106496164B - A kind of dihydrofuran is continuously synthesizing to and the method for isomer separation - Google Patents
A kind of dihydrofuran is continuously synthesizing to and the method for isomer separation Download PDFInfo
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/28—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
It is continuously synthesized the present invention provides a kind of dihydrofuran and the method for isomer separation, includes the following steps: that raw material butylene glycol is pumped into preheater, enter back into superheater, reactor；Cyclization reaction obtains the mixture of dihydrofuran and water, by preheater and condenser, into transfer tank, and enters in the middle part of first rectifying column；First rectifying column tower bottom produces unreacted butylene glycol, and overhead extraction mixing dihydrofuran enters in the middle part of Second distillation column；Second distillation column overhead extraction furans, tower middle part produce 2,3-dihydrofuran, and tower bottom produces 2,5-dihydrofuran fraction, and is pumped into the middle part of third distillation column；The azeotropic mixture of third distillation column stripping section side take-off waste water, tower bottom extraction waste liquid, overhead extraction 2,5-dihydrofuran and water enters in the middle part of the 4th rectifying column；4th the top of the distillation column produces finished product 2,5- dihydrofuran.The present invention will synthesize together with separation coupling, have the advantages that continuous production, high-efficient, low energy consumption, good product quality.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of dihydrofuran is continuously synthesizing to and isomer separation
Method.
Background technique
Dihydrofuran is that one kind is widely used in pesticide, medicine, a kind of important fine chemicals in the field of polymers, dihydro furan
It mutters and is divided into two kinds of isomers of 2,3-dihydrofuran and 2,5-dihydrofuran, about 10 DEG C of boiling-point difference；Due to olefinic double bonds position
Difference keeps two kinds of isomer nature differences very big, and then leads to two kinds of products as intermediate and can synthesize a large amount of differences
The organic fine chemicals of miscellaneous various Various Functions.Dihydrofuran chemical synthesis at present is using butadiene monoxide as raw material system
2,3-dihydrofuran is taken, then isomerization generates 2,5-dihydrofuran, is isolated 2,5-dihydrofuran by rectifying, the method
More in the presence of synthesis side reaction, isomerisation conversion is low, and material is easy polymerization, and two kinds of isomers of separation need process in industrial production
More, product purity is low for separation, and isolation technics difficulty is larger, causes two kinds of isomers prices of dihydrofuran high, and then constrain
Development and utilization of the dihydrofuran in fine chemicals.
Dihydrofuran: English name dihydrofuran, dihydrofuran include two kinds of isomers, Chinese: 2,
3- dihydrofuran and 2,5-dihydrofuran, the now characteristic of two kinds of products of summary and the application in fine chemicals industry.
2,5-dihydrofuran, colourless transparent liquid, English name: 2,5-dihydrofuran, No. CAS: 1708-29-8,
Molecular formula: C4H6O, molecular weight: 70.09, relative density 0.927g/ml, 65 DEG C of boiling point, -24 DEG C of flash-point.With 2,5- dihydrofuran
For starting material, synthesis 3- tetrahydrofurfuryl carbinol can be synthesized, and then synthesizes dinotefuran, the process route is succinct, and wastewater flow rate is small,
Safety and environmental protection, therefore 2,5-dihydrofuran is to synthesize an important intermediate of dinotefuran pesticide.
Dinotefuran (dinotefuran) is the super nicotinic insecticide of latest generation.Itself and existing nicotinic insecticide
Chemical structure be it is far from each other, its tetrahydrofuran base is free of instead of pervious chloro-pyridine base, chloro-thiazole base
Halogen.Meanwhile it is also different with nicotine in aspect of performance, insecticidal spectrum is wider, so, people are referred to as " furan at present
Mutter nicotine " its toxicity: dinotefuran is fool proof to mammal, and acute oral LD50 is male rat 2450mg/kg, female
Rat 2275mg/kg；Male mice 2840mg/kg, female mice 2000mg/kg.LD50 > 2000mg/ percutaneous to rat acute
Kg (female, male).Without teratogenesis, carcinogenic and mutagenicity.Dinotefuran is also fool proof to aquatile.Ichthyotoxin test shows furan worm
Amine is to carp nm (48h) > 1000mg/L, to water flea > 1000mg/L.Equally, dinotefuran is also very low to birds toxicity, to quail urgency
Property LD50 of passing through mouth > 1000mg/kg.Through learning to honeybee test, dinotefuran does not influence honeybee producting honey to honeybee safety.
Dinotefuran medicament is developed by Mitsui Chemical Co., Ltd., is ultra high efficiency insecticide of new generation, have tag,
Stomach toxicity and root absorbability is strong, quick-acting height, lasting period 4-8 weeks long (theoretical lasting effect 43 days), the features such as insecticidal spectrum is wide, and it is right
Sucking insect has excellent preventive effect, and shows very high insecticidal activity in very low dosage.Compared to the first and second generation desinsection
Agent, insecticidal spectrum is wider, using more convenient, can overcome one or two generation insecticide bring resistance risks.Be mainly used for prevent and treat wheat,
Aphid, leafhopper, plant hopper, thrips, aleyrodid and its resistant strain in the various crops such as rice, cotton, vegetables, fruit tree, tobacco leaf, together
When have efficiently to coleoptera, Diptera and Lepidoptera, Diptera, beetle mesh and total wing mesh insect, and to blattaria, termite, housefly
Equal sanitary insect pests have efficiently.
2,3-dihydrofuran is a kind of chemical substance, English alias: 2,3-DHF, molecular weight: and 70.09, molecular formula is
Boiling point: C4H6O 55.2 DEG C, density 0.927g/ml, is used for organic synthesis solvent, electronic chemical product, Special Resin, synthetic perfume
Deng being particularly used as the important source material of the pharmaceutical chemicals such as 7- ethyl tryptophol, different support polyacid.
It is Material synthesis 7- ethyl tryptophol by 2,3-dihydrofuran and adjacent ethyl hydrazinobenzene hydrochloride salt, product yield reaches 70%
More than, 90% or more crude product purity, fine work purity can reach 99% after purification, and the technological operation is simple, be current industrial metaplasia
Produce principal synthetic routes.7- ethyl tryptophol also known as 7- ethyl -3- indoles ethyl alcohol；7- ethyl group tryptophol；7- ethyl -3- ethoxy Yin
Diindyl；7- ethyl tryptosol, 7- ethyl tryptophol are the key that synthesis non-steroidal anti-inflammatory analgesics Etodolac (etodolac) is intermediate.
Etodolac is non-steroidal anti-inflammatory drugs, can be with relief from osteoarthritis (degenerated joint lesion), rheumatoid arthritis
Sings and symptoms.Relieve pain symptom.Rheumatoid arthritis, including the distinctive bone defect of the disease (erosion), articular cavity is narrow
It is narrow, osteoarthritis (degenerative joint disease) and mild to moderate pain.
Etodolac is non-steroidal anti-inflammatory drugs, has anti-inflammatory, antipyretic and analgesic activity.Its mechanism of action may be by hindering
The activity of abscission ring oxygenase, to inhibit the synthesis of prostaglandin (PG).This product is nonsteroid anti-inflammatory drugs (NSAIDs).Make
It can be with aspirin, other antalgesics and many most common prescription NSAIDs phases for analgesia and anti-inflammatory drug, curative effect
Than.It selectively inhibits prostaglandin biosynthesis in inflammation part, when giving rat therapeutic dose, to stomach prostaglandin
The inhibition of PGE2 is slight and of short duration.This may be the lesser mechanism of its gastrointestinal side effect.Rat assist agent arthritis mould
Type shows that this product can reduce the incidence and seriousness of bone and joint damage, and the progress of energy reverse disease.Animal experiment has no
Teratogenesis has smaller influence to fertility and reproductive function.But animal pregnancy is experiments have shown that inhibit prostaglandin biology to close
At drug can cause have difficult labour and give a birth delay.The inhibitor of certain prostaglandin biosynthesis may interfere with closing for arterial duct
It closes.
Chinese patent CN99111312.8 makes 1,4-butanediol and H-ZSM-5 molecular sieve catalyst at 170~250 DEG C
Contact, is reacted and is collected product, and the preparation method of the tetrahydrofuran provided is keeping high feed stock conversion and tetrahydro furan
Under conditions of selectivity of muttering, the processing capacity of 1,4-butanediol is significantly improved, every gram of catalyst can handle Isosorbide-5-Nitrae-fourth per hour
100~1300 grams of glycol, to the selectivity of tetrahydrofuran up to 99.5% or more.This method is not suitable with butylene glycol cyclization and produces
Dihydrofuran, reason are that butylene glycol contains active olefin double bond, and liquid-solid catalytic reaction stay time, polymerism is serious,
Side reaction is more, and crotonaldehyde production quantity is big, and smell weight, reaction yield is low, and separation dihydrofuran purity is lower, and industrialization difficulty is big.
Summary of the invention
Extensive use in view of dihydrofuran in fields such as medicine, pesticide, materials, dihydrofuran synthesis and isomer separation
Purifying is the direct exploitation and cost for restricting downstream product, and the invention patent provides a kind of dihydrofuran and is continuously synthesizing to and isomery
The method of body separation, uses Isosorbide-5-Nitrae-butylene glycol for raw material, obtains mixing for dihydrofuran and water by gas-solid catalysis cyclization reaction
Object is closed, then by two kinds of isomers of separation and purification 2,3-dihydrofuran and 2,5-dihydrofuran, significantly reduces dihydrofuran
Production cost.
The technical proposal for solving the technical problem of the invention are as follows:
A kind of dihydrofuran is continuously synthesizing to and the method for isomer separation, includes the following steps:
(1) it will be added in head tank containing Isosorbide-5-Nitrae-butylene glycol mixed raw material, then be pumped into preheater and preheat through raw material
To 80-120 DEG C, the raw material after preheating, which enters back into, is superheated to 140-300 DEG C in superheater, gained gaseous phase materials enter reactor
In, under high-performance solid catalyst action, in 150-300 DEG C, gas phase dihydro is obtained after gas and solid phase catalyzing normal pressure or decompression are anti-
The Synthesis liquid of furans and water, the reaction velocity are 0.5-2.5/h, and the vacuum degree of the Depressor response is 0~0.08MPa.Instead
Answering total conversion is 95~99%, leaves the gaseous substance composition of reactor are as follows: (the furan containing 2,3- tetrahydro of dihydrofuran 60~65%
It mutters and 2,5- tetrahydrofuran), water 15~18%, butylene glycol 10~20%, furans 1~3%, crotonaldehyde 0.1~0.3%, 3-
Hydroxyl tetrahydrofuran 0.1~0.5%, butyrolactone 0.1~0.3%, octenal 0.1~0.3%, the ratio of two kinds of isomers are 2,
3- tetrahydrofuran: 2,5- tetrahydrofuran mass values=1:1~10.Pyroreaction 2,3-dihydrofuran ratio is high, low-temp reaction
2,5- dihydrofuran ratio is high.
(2) Synthesis liquid of gas phase dihydrofuran and water obtained by step (1) sequentially enters preheater and condenser, is cooled to
After 20-30 DEG C, it is delivered in the middle part of first rectifying column into raw material transfer tank, then through delivery pump I, is collected in first rectifying column tower bottom
Unreacted Isosorbide-5-Nitrae-butylene glycol, and be back in superheater by delivery pump II, first rectifying column overhead collection mixes dihydro
Furans fraction, and be delivered in the middle part of Second distillation column；
(3) Second distillation column overhead extraction furans, rectifying column middle part produce 2,3-dihydrofuran finished product, tower bottom extraction 2,5-
Dihydrofuran heavy constituent, the fraction are pumped into the middle part of third distillation column by delivery pump III；
(4) third distillation column tower bottom is by III serialization of delivery pump extraction rectifying waste liquid and through subsequent environmental protection treatment, side line
Gas phase extracted waste water enters the 4th rectifying through biochemical treatment, the azeotropic mixture of overhead extraction 2,5-dihydrofuran and water, the azeotropic mixture
In the middle part of tower；
(5) the 4th rectifying columns use Isosorbide-5-Nitrae-butylene glycol extracting rectifying, overhead extraction finished product 2,5-dihydrofuran, and tower bottom is adopted
Aqueous 1,4- butylene glycol out.
Preferably, mixed raw material described in step (1) is by including following parts by weight component: Isosorbide-5-Nitrae-butylene glycol 90~
99 parts and 0~9 part of 1,4- butanediol.
Preferably, reactor described in step (1) is tubular fixed-bed catalytic reactor, inside is equipped with expansion joint.
Reactor in the prior art uses tank reactor, consolidates catalysis process using liquid, and the reaction time is long, and side reaction is more, and polymerization is existing
As serious, crotonaldehyde production quantity is big, and smell weight, difficulty of governance is big, and reaction yield is low, and separation dihydrofuran purity is lower, industry
It is larger to change difficulty, the present invention uses fixed bed reactors, prepares dihydrofuran through gas solid catalytic reaction, side reaction is few, crotonaldehyde
Production quantity is few, gained dihydrofuran purity is high.Fixed bed reactors are also known as packed bed reactor, and bed is stationary, and fluid is logical
Bed is crossed to be reacted；Solid catalyst is imitated in the built-in raising of reactor, and by catalyst bed gas-solid phase reaction occurs for material；Column
Tubular fixed-bed reactor is made of more reaction tube parallel connections.Catalyst is set in pipe or between pipe, and thermophore flows through between pipe or in pipe
It is heated or cooled, for caliber usually between 25~50mm, pipe number can up to up to ten thousand.The advantages of fixed bed reactors, is:
1. back-mixing is small, fluid can be contacted effectively with catalyst, can be obtained when reaction is with series connection side reaction more highly selective.2. urging
Agent mechanical loss is small.3. structure is simple.
Preferably, catalyst described in step (1) be support type acid-exchange resin, carried heteropoly acid and Y,
β, type ZSM 5 molecular sieve, support type acid-exchange resin or suported superacid.
Preferably, first rectifying column number of theoretical plate sum described in step (2) is 16~25 pieces, wherein rectifying section reason
It is 10~15 pieces by plate number, stripping section number of theoretical plate is 6~10 pieces；First rectifying column operating condition are as follows: vacuum degree 0~
0.08MPa, 5~75 DEG C of tower top temperature, 150~240 DEG C of column bottom temperature, reflux ratio R=0.5~3, butylene glycol in overhead fraction
Content≤0.01%, water content 0.1~5.0% in tower bottom heavy constituent.
Preferably, Second distillation column described in step (3) is next door rectifying column pattern, Second distillation column theoretical plate sum
It is 70~86 pieces, wherein 15~20 pieces of theoretical number of plates of rectifying section, stripping section number of theoretical plate is 20~26 pieces, and partition wall section is theoretical
35~40 pieces of plate number；Second distillation column operating condition are as follows: atmospheric operation, reflux ratio R=30~60.32~50 DEG C of tower top temperature,
Produce furans fraction, product purity 5~99%；0~54.5 DEG C of temperature in tower, extraction 2,3-dihydrofuran, product purity >=
99%, moisture≤0.05%；66~75 DEG C of column bottom temperature, 2,5-dihydrofuran heavy constituent fraction is produced, wherein 2,3- dihydro furans
It mutters content≤0.05%, moisture 20~35%.
Preferably, third distillation column number of theoretical plate sum described in step (4) is 30~40 pieces, wherein rectifying section reason
It is 20~25 pieces by plate number, stripping section number of theoretical plate is 10~15 pieces, and Second distillation column charging addition auxiliary agent, auxiliary agent is sodium hydrosulfite
Or 2,6- di-tert-butyl-4-methy phenol；Third distillation column operating condition are as follows: atmospheric operation, reflux ratio R=1.0~1.5, tower
65 DEG C of temperature, 102~170 DEG C of column bottom temperature, 102~105 DEG C of side take-off temperature of top.Tower top 2,5- dihydrofuran azeotropic mixture evaporates
Point: purity 96~99.9%, moisture 0~4%, tower bottom heavy constituent waste liquid aqueous 10~30%, side line waste water: 2,5-dihydrofuran
Content≤0.01%, the organic matter after layering import waste liquid and carry out environmental protection treatment.
Preferably, the 4th rectifying column number of theoretical plate sum described in step (5) is 45~55 pieces, wherein rectifying purification
Section number of theoretical plate is 3~5 pieces, and extraction section number of theoretical plate is 25~30 pieces, 15~20 pieces of stripping section number of theoretical plate；4th rectifying column
Operating condition are as follows: atmospheric operation, reflux ratio R=1.0~1.5, solvent is than 0.5~1；1,66 DEG C of tower top temperature, column bottom temperature 150
~170 DEG C, tower top is high-pure anhydrous 2,5-dihydrofuran product: purity 96~99.9%, moisture≤0.05%, tower bottom extract liquor
Aqueous 5~10%, tower bottom extract liquor is entered in the gasification superheater of synthesis procedure without cooling by delivery pump, without being extracted
Take agent to regenerate, energy conservation and shorten the technological process of production.
Preferably, the first rectifying column is serialization rectifying column；Second distillation column is divided-wall distillation column, the same to time-division
From three kinds of furans, 2,3-dihydrofuran and crude product 2,5-dihydrofuran fractions, since reaction generation furans amount is less, 2,3- dihydros
Furans is fewer than 2,5-dihydrofuran content, therefore does not use conventional two tower clastotypes, using next door rectifying mode, overhead extraction furan
It mutters fraction, 2,3-dihydrofuran finished product is produced in tower, tower bottom produces crude product 2,5-dihydrofuran and enters third distillation column by pump；
Third distillation column is serialization rectifying column, and the 4th rectifying column is extracting rectifying tower, and tower bottom reboiler is all made of pump forced circulation
Heating, to prevent heat exchanger blocking；Overhead condenser is all made of recirculated water and chilled water twin-stage is cooling, reduces exhaust emissions amount.
Compared with prior art, the present invention its remarkable advantage are as follows:
1, chemical reaction forms continuous production process, improves production efficiency, product together with rectifying separation coupling
Conversion ratio and high income, gained 2,5-dihydrofuran product purity are 96~99.9%, moisture≤0.05%；Gained 2,3- dihydro
Furans product purity >=99%, moisture≤0.05%.
2, Second distillation column is divided-wall distillation column, can separate furans, 2,3-dihydrofuran and crude product 2,5- bis- simultaneously
Three kinds of fractions of hydrogen furans, since reaction generates, furans amount is less, and 2,3-dihydrofuran is fewer than 2,5-dihydrofuran content, therefore uses
Two conventional tower clastotypes of divided-wall distillation column substitution, reduce production process, have biggish economic benefit.
3, the 4th rectifying column uses extractive distillation column to use raw material butylene glycol for extractant, anhydrous 2, the 5- bis- of overhead extraction
Hydrogen furans, tower bottom produce aqueous butylene glycol, without carrying out regeneration treatment to it, are pumped directly into process synthesis material tank, recycle
It uses, reduces wastewater treatment process.
4, dihydrofuran provided by the present invention is continuously synthesizing to and the method for isomer separation, is suitable for Isosorbide-5-Nitrae-butylene two
The raw material of alcohol content 90~99% requires low, wide adaptation range to product purity, helps to reduce production cost.
5, method provided by the present invention, gained waste water COD significantly reduce, can directly carry out biochemical treatment, prevent technique
Harm, improves efficiency of energy utilization.
Specific embodiment
In order to which technical solution of the present invention and advantage is more clearly understood, with reference to embodiments to the present invention carry out into
One step is described in detail.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to limit this hair
It is bright.
Embodiment 1
(1) by mixed raw material (Isosorbide-5-Nitrae-butylene glycol 90~99%, 1,4-butanediol 0~9%, Isosorbide-5-Nitrae-butynediols 0~
4%；Water: propilolic alcohol 0.1~0.2% 0.1~5%) is added in head tank, then is pumped into preheater through raw material and is preheated to 80-
120 DEG C, the raw material after preheating, which enters back into, is superheated to 140-300 DEG C in superheater, gained gaseous phase materials enter in reactor, are urging
Under the effect of agent Y type molecular sieve, in 150-300 DEG C, through gas and solid phase catalyzing normal pressure or Depressor response to gas phase dihydrofuran and water
Synthesis liquid, the reaction velocity is 0.5-2.5/h, and the vacuum degree of the Depressor response is 0~0.08MPa；The Synthesis liquid
Composition are as follows: dihydrofuran 60~65% (contains 2,3- tetrahydrofuran and 2,5- tetrahydrofuran), water 15~18%, butylene glycol 10~
20%, furans 1~3%, crotonaldehyde 0.1~0.3%, 3- hydroxyl tetrahydrofuran 0.1~0.5%, butyrolactone 0.1~0.3% is pungent
Olefine aldehydr 0.1~0.3%；
(2) Synthesis liquid of gas phase dihydrofuran and water obtained by step (1) sequentially enters preheater and condenser, is cooled to
After 20-30 DEG C, it is delivered in the middle part of first rectifying column into raw material transfer tank, then through delivery pump I, is collected in first rectifying column tower bottom
Unreacted Isosorbide-5-Nitrae-butylene glycol (content is 85~95%), and be back in superheater by delivery pump II, first rectifying column
Overhead collection mixes dihydrofuran fraction, and is delivered in the middle part of Second distillation column.The first rectifying column number of theoretical plate sum is
16~25 pieces, wherein theoretical number of plates of rectifying section is 10~15 pieces, and stripping section number of theoretical plate is 6~10 pieces；First rectifying column operation
Condition are as follows: 0~0.08MPa of vacuum degree, 5~75 DEG C of tower top temperature, 150~240 DEG C of column bottom temperature, reflux ratio R=0.5~3；
(3) Second distillation column overhead extraction furans, purity are 50~99.5%, produce 2,3-dihydrofuran in the middle part of rectifying column
Finished product, purity 99.5%, tower bottom produce 2,5-dihydrofuran heavy constituent (purity 50~75%), which is pumped by delivery pump III
Enter in the middle part of third distillation column.Second distillation column is next door rectifying column pattern, and Second distillation column theoretical plate sum is 70~86 pieces,
In, 15~20 pieces of theoretical number of plates of rectifying section, stripping section number of theoretical plate is 20~26 pieces, 35~40 pieces of partition wall section number of theoretical plate；
Second distillation column operating condition are as follows: atmospheric operation, reflux ratio R=30~60, produce furans fraction by 32~50 DEG C of tower top temperature；
Temperature~54.5 DEG C in tower produce 2,3-dihydrofuran；66~75 DEG C of column bottom temperature, extraction 2,5-dihydrofuran recombination fractionation
Point.
(4) third distillation column tower bottom is by III serialization of delivery pump extraction rectifying waste liquid and through subsequent environmental protection treatment, side line
Gas phase extracted waste water is through biochemical treatment (containing crotonaldehyde 0.01~0.3%), the azeotropic mixture of overhead extraction 2,5-dihydrofuran and water
(purity 96~99.5%, aqueous 0~5%), the azeotropic mixture enter in the middle part of the 4th rectifying column.Third distillation column number of theoretical plate sum
It is 30~40 pieces, wherein theoretical number of plates of rectifying section is 20~25 pieces, and stripping section number of theoretical plate is 10~15 pieces, Second distillation column
Charging addition auxiliary agent, auxiliary agent are sodium hydrosulfite or 2,6- di-tert-butyl-4-methy phenol；Third distillation column operating condition are as follows: normal pressure
Operation, reflux ratio R=1.0~1.5,65 DEG C of tower top temperature, 102~170 DEG C of column bottom temperature, side take-off temperature 102~105
℃。
(5) the 4th rectifying columns use extractant Isosorbide-5-Nitrae-butylene glycol extracting rectifying, solvent ratio (extraction dosage: inlet amount matter
Measure ratio) 0.5~1:1, overhead extraction finished product 2,5-dihydrofuran (purity 96~99.5%, aqueous≤0.05%), tower bottom extraction
Aqueous 1,4- butylene glycol (0~5%).4th rectifying column number of theoretical plate sum is 45~55 pieces, wherein rectifying clean-up stage is theoretical
Plate number is 3~5 pieces, and extraction section number of theoretical plate is 25~30 pieces, 15~20 pieces of stripping section number of theoretical plate；The operation article of 4th rectifying column
Part are as follows: atmospheric operation, reflux ratio R=1.0~1.5, solvent is than 0.5~1；1,66 DEG C of tower top temperature, column bottom temperature 150~170
℃。
Embodiment 2
Operated with embodiment 1 it is identical, unlike separative unit stop using the 4th rectifying column, raw material is directly entered raw material
Tank, by reacting and separating, extraction obtains 2,3-dihydrofuran in the middle part of Second distillation column, and extraction obtains 2 at the top of third distillation column,
5- dihydrofuran, gained 2,3-dihydrofuran product purity >=99%, water content≤4.5%；Gained 2,5- dihydrofuran product
Purity >=96%.
Embodiment 3
Raw material group becomes Isosorbide-5-Nitrae-butylene glycol purity >=98.5%, Isosorbide-5-Nitrae-butynediols purity≤1.2%, 1,4-butanediol
Purity≤0.1%, propilolic alcohol 0.1~0.2%, moisture 0.1~0.2%
Using the identical operation of embodiment 1, the difference is that synthesis reactor uses low-temp reaction, reaction temperature 150~250
DEG C, it is synthetically produced ability increase, produces finished product 2,3-dihydrofuran, four rectifying of purity >=99.5%, the in the middle part of Second distillation column
Top of tower extraction finished product 2,5-dihydrofuran, purity 99.5%, third distillation column side take-off waste water crotons aldehyde≤
0.1%, 10000~20000mg/L of COD value of waste water, subsequent wastewater treatment difficulty are reduced.
Embodiment 4
Raw material forms situation: Isosorbide-5-Nitrae-butylene glycol purity >=99%, Isosorbide-5-Nitrae-butynediols purity≤0.5%, Isosorbide-5-Nitrae-fourth two
Alcohol purity≤2~3%, propilolic alcohol 0.1~0.2%, moisture≤0.05%
Operating process uses pyroreaction, 250~300 DEG C of reaction temperature, is synthetically produced with embodiment 1, synthesis reactor
Ability increases, and finished product 2,3-dihydrofuran, purity >=99.5% are produced in the middle part of Second distillation column, and antioxygen auxiliary agent is not added in rectifying column；
Finished product 2,5-dihydrofuran, purity 97~98%, third distillation column side take-off waste water crotonaldehyde are produced at the top of 4th rectifying column
Content 0.5~1.5%, 50000~100000mg/L of COD value of waste water, subsequent wastewater treatment difficulty increase；Using high―temperature nuclei two
Hydrogen furans, 2,3-dihydrofuran yield increase, and the ratio after 2,3-dihydrofuran and 2,5-dihydrofuran reaction can reach 1:1 ratio
Example
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (8)
1. a kind of dihydrofuran continuous production and isolated device, which is characterized in that described device includes head tank (1), mistake
Hot device (2), reactor (3), preheater (4), condenser (5), raw material pump (6), transfer tank (7), the first delivery pump (8), first
Rectifying column (10), Second distillation column (11), third delivery pump (12), third distillation column (13), the 5th delivery pump (15) and the 4th
Rectifying column (16)；
The superheater (2) is fixed tubular heat exchanger, and heat medium is high temperature heat transfer oil, and wherein material walks tube side, leads
Hot oil walks shell side；
The preheater (4) is fixed tubular heat exchanger, and raw material walks shell side, and synthesis gaseous phase materials walk tube side；
The reactor (3) is tubular fixed-bed catalytic reactor, inside sets expansion joint, and heat medium is high temperature in heat exchanging pipe
Conduction oil；
The head tank (1), raw material pump (6) are successively sequentially connected with the shell side feed inlet of preheater (4), the shell of preheater (4)
Journey discharge port, superheater (2) are successively sequentially connected with the feed inlet of reactor (3) bottom, the discharge port at the top of reactor (3) with
The tube side feed inlet of preheater (4) is connected, the tube side discharge port of preheater (4), condenser (5), transfer tank (7), the first conveying
Pump (8) is successively sequentially connected with the middle part feed inlet of first rectifying column (10), the top discharge mouth of the first rectifying column (10)
It is connected with the middle part feed inlet of Second distillation column (11), the bottom discharge port of the Second distillation column (11), third delivery pump
(12) successively sequentially it is connected with the middle part feed inlet of third distillation column (13), the top discharge mouth and the 4th of third distillation column (13)
The middle part feed inlet of rectifying column (16) is connected, and the bottom discharge port of third distillation column (13) is connected with the 5th delivery pump (15).
2. dihydrofuran continuous production as described in claim 1 and isolated device, which is characterized in that described device further includes
Second delivery pump (9), the tube side feed inlet of the bottom discharge port of first rectifying column (10), the second delivery pump (9) and superheater (2)
Successively sequence is connected.
3. dihydrofuran continuous production as claimed in claim 1 or 2 and isolated device, which is characterized in that described device is also
Wrap the 4th delivery pump (14), the side of the bottom discharge port of the 4th rectifying column (16), the 4th delivery pump (14) and head tank (1) into
Material mouth is successively sequentially connected.
4. dihydrofuran continuous production as described in claim 1 and isolated device, which is characterized in that the first rectifying column
It (10) is serialization rectifying column, Second distillation column (11) is divided-wall distillation column, and third distillation column (13) is serialization rectifying column,
4th rectifying column (16) is extracting rectifying tower, and tower bottom reboiler is all made of pump forced circulation heating, and overhead condenser is all made of
Recirculated water and chilled water twin-stage are cooling.
5. dihydrofuran continuous production and isolated device as described in claim 1 or 4, which is characterized in that first essence
Evaporate tower (10) number of theoretical plate sum be 16 ~ 25 pieces, wherein theoretical number of plates of rectifying section be 10 ~ 15 pieces, stripping section number of theoretical plate be 6 ~
10 pieces.
6. dihydrofuran continuous production and isolated device as described in claim 1 or 4, which is characterized in that second essence
Evaporating tower (11) is next door rectifying column pattern, and Second distillation column theoretical plate sum is 70 ~ 86 pieces, wherein theoretical number of plates of rectifying section 15 ~
20 pieces, stripping section number of theoretical plate is 20 ~ 26 pieces, 35 ~ 40 pieces of partition wall section number of theoretical plate.
7. dihydrofuran continuous production and isolated device as described in claim 1 or 4, which is characterized in that the third essence
Evaporating tower (13) number of theoretical plate sum is 30 ~ 40 pieces, wherein theoretical number of plates of rectifying section is 20 ~ 25 pieces, and stripping section number of theoretical plate is 10
~ 15 pieces.
8. dihydrofuran continuous production and isolated device as described in claim 1 or 4, which is characterized in that the 4th essence
Evaporating tower (16) number of theoretical plate sum is 45 ~ 55 pieces, wherein rectifying clean-up stage number of theoretical plate is 3 ~ 5 pieces, and extraction section number of theoretical plate is
25 ~ 30 pieces, 15 ~ 20 pieces of stripping section number of theoretical plate.
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| CN110437180A (en) * | 2019-07-19 | 2019-11-12 | 海利尔药业集团股份有限公司 | A kind of method that UF membrane coupling cyclization reaction prepares 2,5- dihydrofuran |
Citations (3)
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|---|---|---|---|---|
| CN1223645A (en) * | 1996-05-03 | 1999-07-21 | 伊斯曼化学公司 | Continuous process for the conversion of 2,5-dihydrofuran to 2,3-dihydrofuran |
| CN101622237A (en) * | 2007-03-06 | 2010-01-06 | 可乐丽股份有限公司 | Method for continuously producing 2,5-dihydrofuran |
| CN102633754A (en) * | 2012-03-28 | 2012-08-15 | 南开大学 | Method for preparing high-purity 2, 5-dihydrofuran by modified nano alumina catalyst |
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| CN1223645A (en) * | 1996-05-03 | 1999-07-21 | 伊斯曼化学公司 | Continuous process for the conversion of 2,5-dihydrofuran to 2,3-dihydrofuran |
| CN101622237A (en) * | 2007-03-06 | 2010-01-06 | 可乐丽股份有限公司 | Method for continuously producing 2,5-dihydrofuran |
| CN102633754A (en) * | 2012-03-28 | 2012-08-15 | 南开大学 | Method for preparing high-purity 2, 5-dihydrofuran by modified nano alumina catalyst |
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