CN106496164A - A kind of dihydrofuran be continuously synthesizing to and isomer separation method - Google Patents
A kind of dihydrofuran be continuously synthesizing to and isomer separation method Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- 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
The invention provides the method for a kind of continuous synthesis of dihydrofuran and isomer separation, comprises the steps：Raw material butylene glycol pumps into preheater, enters back into superheater, reactor；Ring-closure reaction obtains the mixture of dihydrofuran and water, by preheater and condenser, enters transfer tank, and enters in the middle part of first rectifying column；First rectifying column bottom of towe produces unreacted butylene glycol, and overhead extraction mixing dihydrofuran is entered in the middle part of Second distillation column；Second distillation column overhead extraction furan, produces 2,3 dihydrofuran in the middle part of tower, bottom of towe produces 2,5 dihydrofuran fractions, and pumps in the middle part of third distillation column；Third distillation column stripping section side take-off waste water, bottom of towe produce waste liquid, and 2,5 dihydrofuran of overhead extraction is entered in the middle part of the 4th rectifying column with the azeotropic mixture of water；4th rectifying column tower top produces 2,5 dihydrofuran of finished product.The present invention will synthesis together with separation coupling, have the advantages that continuous prodution, efficiency high, energy consumption be low, 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 technology
Dihydrofuran is that one kind is widely used in a kind of important fine chemicals, dihydro furan in pesticide, medicine, field of polymer technology
Mutter and be divided into two kinds of isomerss of DHF and DHF, about 10 DEG C of boiling-point difference；Due to olefinic double bonds position
Difference, makes two kinds of isomerss nature differences very big, and then causes two kinds of products synthesize a large amount of differences as intermediate
The different organic fine chemicals of miscellaneous various functions.Dihydrofuran chemosynthesis at present are with butadiene monoxide as raw material system
DHF is taken, and then isomerization generates DHF, DHF is isolated by rectification, the method
Presence synthesis side reaction is more, and isomerisation conversion is low, and material is easily polymerized, and separating two kinds of isomers in commercial production needs operation
More, separation product purity is low, and isolation technics difficulty is larger, causes two kinds of isomer prices of dihydrofuran high, and then constrains
Exploitation of the dihydrofuran in fine chemicals.
Dihydrofuran：English name dihydrofuran, dihydrofuran include two kinds of isomerss, Chinese：2,
3- dihydrofuran and DHF, the now characteristic of two kinds of products of summary and the application in fine chemicals industry.
DHF, 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- dihydros
Furan is initiation material, can synthesize 3- tetrahydrofurfuryl carbinols, and then synthesize MTI-446, and the process route is succinct, waste water
Little, safety and environmental protection is measured, therefore DHF is an important intermediate for synthesizing MTI-446 pesticide.
MTI-446 (dinotefuran) is the super nicotinic insecticide of latest generation.Itself and existing nicotinic insecticide
Chemical constitution be far from each other, its tetrahydrofuran base instead of former chloro-pyridine base, chloro-thiazole base, and not contain
Halogen.Meanwhile, also different with nicotine in aspect of performance, insecticidal spectrum is wider, so, current people are referred to as " furan
Mutter nicotine " its toxicity：MTI-446 is fool proof to mammal, and its acute oral LD50 is male rat 2450mg/kg, female
2275 mg/kg of rat；Male mice 2840mg/kg, female mice 2000mg/kg.To rat acute percutaneous LD50>2000mg/
Kg (female, male).Without teratogenesis, carcinogenic and mutagenicity.MTI-446 is also fool proof to aquatile.Ichthyotoxin test shows, furan worm
Amine is to Cyprinus carpio nm (48 h)>1000mg/L, to water flea>1000mg/L.Equally, MTI-446 is also very low to birds toxicity, to Carnis Coturnicis japonicae
Acute oral LD50> 1000mg/kg.Through learning that MTI-446 is to Apiss safety, and does not affect honeybee producting honey to Apiss test.
MTI-446 medicament is developed by Mitsui KCC, is ultra high efficiency insecticide of new generation, with tagging,
Stomach toxicity and root absorbability is strong, quick-acting high, lasting periods in long 4-8 weeks（Theoretical lasting effect 43 days）, the features such as insecticidal spectrum is wide and right
Sucking insect has excellent preventive effect, and shows very high insecticidal activity in very low dosage.Compare first and second generation parasite killing
Agent, insecticidal spectrum are wider, using more convenient, the resistance risk that a secondary insecticide can be overcome to bring.Be mainly used in prevent and treat Semen Tritici aestivi,
Aphid, leafhopper, plant hopper, thrips, aleyrodid and its resistant strain in the various crops such as Oryza sativa L., Cotton Gossypii, vegetable, fruit tree, Nicotiana tabacum L., with
When coleoptera, Diptera and Lepidoptera, Diptera, beetle mesh and total wing mesh insect are had efficiently, and to cockroach, Coptotermes formosanus Shtrari., housefly
Have efficiently Deng sanitary insect pest.
DHF is a kind of chemical substance, English another name：2,3-DHF, molecular weight：70.09, molecular formula is
C4H6O, boiling point：55.2 DEG C, density 0.927g/ml, for organic synthesiss 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 tryptophols, different support polyacid.
It is Material synthesis 7- ethyl tryptophols by DHF and adjacent ethyl hydrazinobenzene hydrochloride salt, product yield reaches 70%
More than, crude product purity more than 90%, after purification, fine work purity can reach 99%, and the technological operation is simple, is current industrialized production
Principal synthetic routes.7- ethyl tryptophols also known as 7- ethyl -3- indole ethanol；7- ethyl group tryptophols；7- ethyl -3- ethoxy Yin
Diindyl；7- ethyl tryptosols, 7- ethyl tryptophols are synthesized in the middle of the key of non-steroidal anti-inflammatory analgesics etodolac (etodolac).
Etodolac is NSAID (non-steroidal anti-inflammatory drug), can be with relief from osteoarthritis（Degenerated joint pathological changes）, rheumatoid arthritis
Sings and symptoms.Alleviating pain symptom.Rheumatoid arthritiss, including the sick distinctive Cranial defect（Corrode）, articular cavity is narrow
Narrow, osteoarthritis（Degenerative joint disease）And mild to moderate pain.
Etodolac is NSAID (non-steroidal anti-inflammatory drug), with antiinflammatory, antipyretic and analgesic activity.Its mechanism of action may be by hindering
The activity of abscission ring oxygenase, so that inhibit prostaglandin（PG synthesis).This product is nonsteroid anti-inflammatory drugses（NSAIDs）.Make
For analgesia and antibiotic medicine, its curative effect can be with aspirin, other analgesic and many prescription the most frequently used at present NSAIDs phases
Than.It optionally suppresses prostaglandin biosynthesiss in inflammation part, when giving rat therapeutic dose, to stomach prostaglandin
The suppression of PGE2 is slight and of short duration.This is probably the less mechanism of its gastrointestinal side effect.Rat assist agent arthritis mould
Type shows that this product can reduce the incidence rate and seriousness of bone and joint damage, and the progress of energy reverse disease.Animal experiment has no
Teratogenesis, have less impact to fertility and reproductive function.But animal pregnancy test shows to suppress the biological conjunction of prostaglandin
Into medicine can cause difficult labour and childbirth postpone.The biosynthetic inhibitor of some prostaglandins may interfere with closing for ductus arteriosuss
Close.
Chinese patent CN99111312.8 makes BDO and H-ZSM-5 molecular sieve catalysts at 170～250 DEG C
Contact, is reacted and is collected product, there is provided the preparation method of tetrahydrofuran keeping high feed stock conversion and tetrahydrochysene furan
Under the conditions of muttering selectively, the disposal ability of BDO is significantly improved, every gram of catalyst can process Isosorbide-5-Nitrae-fourth per hour
100～1300 grams of glycol, to the selectivity of tetrahydrofuran up to more than 99.5%.The method is not suitable with butylene glycol cyclization system
Dihydrofuran is taken, reason is that butylene glycol contains active olefin double bond, and liquid-solid catalytic reaction stay time, polymerism are tight
Weight, side reaction are more, and crotonic aldehyde growing amount is big, and abnormal smells from the patient weight, reaction yield are low, and separation dihydrofuran purity is relatively low, industrialization difficulty
Greatly.
Content of the invention
In view of extensive application of the dihydrofuran in fields such as medicine, pesticide, materials, dihydrofuran synthesis and isomer separation
Purification is the directly exploitation of restriction downstream product and cost, and patent of the present invention provides a kind of dihydrofuran and is continuously synthesizing to and isomery
The detached method of body, adopts Isosorbide-5-Nitrae-butylene glycol for raw material, obtains dihydrofuran by gas-solid catalysis ring-closure reaction mixed with water
Compound, then by the two kinds of isomers of separation and purification DHF and DHF, significantly reduces dihydrofuran
Production cost.
The present invention solve the technical scheme that adopted of technical problem for：
A kind of dihydrofuran be continuously synthesizing to and isomer separation method, comprise the steps：
(1) mixed material containing Isosorbide-5-Nitrae-butylene glycol is added in head tank, then pumps in preheater through raw material pump and be preheated to
80-120 DEG C, the raw material after preheating is entered back into, and gained gaseous phase materials are entered in reactor,
Under high-performance solid catalyst action, in 150-300 DEG C, after gas and solid phase catalyzing normal pressure or decompression instead, obtain gas phase dihydrofuran
With the Synthesis liquid of water, the reaction velocity is 0.5-2.5/h, and the vacuum of the Depressor response is 0 ~ 0.08MPa.Reaction is total to be turned
Rate is 95 ~ 99%, and the gaseous substance for leaving reactor is consisted of：Dihydrofuran 60 ~ 65%（Tetrahydrofuran containing 2,3- and 2,5- tetra-
Hydrogen furan）, water 15 ~ 18%, butylene glycol 10 ~ 20%, furan 1 ~ 3%, crotonic aldehyde 0.1 ~ 0.3%, 3- hydroxyl tetrahydrofurans 0.1 ~
0.5%, butyrolactone 0.1 ~ 0.3%, octenal 0.1 ~ 0.3%, the ratio of two kinds of isomers is 2,3- tetrahydrofurans：2,5- tetrahydrochysene furans
Mutter mass values=1：1~10.Pyroreaction DHF ratio is high, and low-temp reaction DHF ratio is high.
(2) step (1) gained gas phase dihydrofuran sequentially enters preheater and condenser with the Synthesis liquid of water, is cooled to
After 20-30 DEG C, raw material transfer tank is entered, then is delivered in the middle part of first rectifying column through delivery pump I, collected in first rectifying column bottom of towe
Unreacted Isosorbide-5-Nitrae-butylene glycol, and be back in superheater by delivery pump II, first rectifying column overhead collection mixes dihydro
Furan fraction, and be delivered in the middle part of Second distillation column；
(3) Second distillation column overhead extraction furan, produces DHF finished product in the middle part of rectifying column, bottom of towe produces 2,5- bis-
Hydrogen furan heavy constituent, the fraction are pumped in the middle part of third distillation column by delivery pump III；
(4) third distillation column bottom of towe produces rectification waste liquid and through follow-up environmental protection treatment, side line gas phase by III serialization of delivery pump
Azeotropic mixture of the extracted waste water through biochemical treatment, overhead extraction DHF and water, the azeotropic mixture are entered in the 4th rectifying column
Portion；
(5) the 4th rectifying columns adopt Isosorbide-5-Nitrae-butylene glycol extracting rectifying, overhead extraction finished product DHF, bottom of towe to produce
Aqueous 1,4- butylene glycols.
Preferably, mixed material described in step (1) is by including following parts by weight component：1,4- butylene glycols 90 ~
99 parts and 0 ~ 9 part of 1,4- butanediols.
Preferably, reactor described in step (1) is tubular fixed-bed catalytic reactor, inside is provided with expansion joint.
Reactor of the prior art adopts tank reactor, and using the solid catalysis process of liquid, the response time is long, and side reaction is more, and polymerization is existing
As serious, crotonic aldehyde growing amount is big, abnormal smells from the patient weight, and difficulty of governance is big, and reaction yield is low, and it is relatively low to separate dihydrofuran purity, industry
Change difficulty is larger, and the present invention adopts fixed bed reactors, prepares dihydrofuran through gas solid catalytic reaction, and side reaction is few, crotonic aldehyde
Growing amount is few, and gained dihydrofuran purity is high.Fixed bed reactors lead to also known as packed bed reactor, bed transfixion, fluid
Cross bed to be reacted；Solid catalyst is imitated in the built-in raising of reactor, and material occurs gas-solid phase reaction by beds；Row
Tubular fixed-bed reactor is made up of many reaction tube parallel connections.Catalyst is put in pipe or between pipe, thermophore is flowed through between pipe or pipe is interior
It is heated or cooled, generally between 25～50mm, pipe number can up to up to ten thousand for caliber.The advantage of fixed bed reactors is：
1. back-mixing is little, and fluid can carry out effective contact with catalyst, can obtain compared with high selectivity when reaction is with series connection side reaction.2. urge
Agent mechanical loss is little.3. simple structure.
Preferably, catalyst described in step (1) be support type acid-exchange resin, carried heteropoly acid and Y,
β, ZSM -5 type molecular sieve, support type acid-exchange resin or suported superacid.
Preferably, the sum of first rectifying column number of theoretical plate described in step (2) is 16 ~ 25 pieces, wherein, rectifying section is theoretical
Plate number is 10 ~ 15 pieces, and profit reduction and reserving section number of theoretical plate is 6 ~ 10 pieces；First rectifying column operating condition is：0 ~ 0.08MPa of vacuum, tower
5 ~ 75 DEG C of the temperature in top, 150 ~ 240 DEG C of column bottom temperature, reflux ratio R=0.5 ~ 3, butylene glycol content≤0.01% in overhead fraction, tower
Water content 0.1 ~ 5.0% in the heavy constituent of bottom.
Preferably, Second distillation column described in step (3) is next door rectifying column pattern, Second distillation column theoretical plate sum
For 60 ~ 70 pieces, wherein, 15 ~ 20 pieces of theoretical number of plates of rectifying section, profit reduction and reserving section number of theoretical plate are 20 ~ 26 pieces, partition wall section number of theoretical plate
35 ~ 40 pieces；Second distillation column operating condition is：Atmospheric operation, reflux ratio R=30 ~ 60.32 ~ 50 DEG C of tower top temperature, produces furan
Fraction, product purity 5 ~ 99%；0 ~ 54.5 DEG C of temperature in tower, extraction DHF, product purity >=99%, moisture≤
0.05%；66 ~ 75 DEG C of column bottom temperature, produces DHF heavy constituent fraction, wherein DHF content≤0.05%,
Moisture 20 ~ 35%.
Preferably, the sum of third distillation column number of theoretical plate described in step (4) is 30 ~ 40 pieces, wherein, rectifying section is theoretical
Plate number is 20 ~ 25 pieces, and profit reduction and reserving section number of theoretical plate is 10 ~ 15 pieces, and auxiliary agent is added in Second distillation column charging, and auxiliary agent is sodium hydrosulfite or 2,
6- di-tert-butyl-4-methy phenols；Third distillation column operating condition is：Atmospheric operation, reflux ratio R=1.0 ~ 1.5, tower top temperature
65 DEG C, 102 ~ 170 DEG C of column bottom temperature, 102 ~ 105 DEG C of side take-off temperature.Tower top 2,5- dihydrofuran azeotropic mixture fractions：Purity
96 ~ 99.9%, moisture 0 ~ 4%, bottom of towe heavy constituent waste liquid aqueous 10 ~ 30%, side line waste water：DHF content≤0.01%,
Organic substance after layering imports waste liquid and carries out environmental protection treatment.
Preferably, the sum of the 4th rectifying column number of theoretical plate described in step (5) is 45 ~ 55 pieces, wherein, rectification 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；4th rectifying column is operated
Condition is：Atmospheric operation, reflux ratio R=1.0 ~ 1.5, solvent is than 0.5 ~ 1；1,66 DEG C of tower top temperature, 150 ~ 170 DEG C of column bottom temperature,
Tower top is high-pure anhydrous 2,5- dihydrofuran product：Purity 96 ~ 99.9%, moisture≤0.05%, bottom of towe extract aqueous 5 ~ 10%,
Bottom of towe extract is entered in the gasification superheater of synthesis procedure, without carrying out extractant regeneration by delivery pump without cooling, section
And the technological process of production can be shortened.
Preferably, the first rectifying column is serialization rectifying column；Second distillation column is divided-wall distillation column, the same to time-division
From furan, three kinds of fractions of DHF and crude product DHF, due to reaction less, 2, the 3- dihydros that generate furan amount
Furan is fewer than DHF content, therefore does not adopt conventional two tower clastotypes, using next door rectification mode, overhead extraction furan
Mutter fraction, in tower, produce DHF finished product, bottom of towe extraction crude product DHF 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 using pump forced circulation
Heating, to prevent heat exchanger to block；Overhead condenser is cooled down using recirculated water and chilled water twin-stage, reduces exhaust emissions amount.
Compared with prior art, its remarkable advantage is the present invention：
1st, chemical reaction constitutes continuous prodution flow process together with rectification separation coupling, improves production efficiency, and product is converted
Rate and high income, gained DHF product purity are 96 ~ 99.9%, moisture≤0.05%；Gained 2,3 dihydro furan is produced
Product purity >=99%, moisture≤0.05%.
2nd, Second distillation column is divided-wall distillation column, can concurrently separate furan, DHF and crude product 2,5- bis-
Three kinds of fractions of hydrogen furan, as reaction is generated, furan amount is less, and DHF is fewer than DHF content, therefore adopts
Divided-wall distillation column substitutes two conventional tower clastotypes, reduces production process, with larger economic benefit.
3rd, the 4th rectifying column adopts extractive distillation column to adopt raw material butylene glycol for extractant, anhydrous 2, the 5- bis- of overhead extraction
Hydrogen furan, bottom of towe produce aqueous butylene glycol, without the need for carrying out Regeneration Treatment to which, are pumped directly into operation synthesis material tank, circulate
Use, reduce wastewater treatment operation.
4th, dihydrofuran provided by the present invention be continuously synthesizing to and isomer separation method, it is adaptable to Isosorbide-5-Nitrae-butylene two
The raw material of alcohol content 90 ~ 99%, requires low, wide accommodation to product purity, contributes to reducing production cost.
5th, method provided by the present invention, gained waste water COD are significantly reduced, and directly can be carried out biochemical treatment, be prevented technique
Harm, improves efficiency of energy utilization.
Specific embodiment
In order that technical scheme and advantage become more apparent, with reference to embodiments the present invention is entered to advance
One step is described in detail.It should be appreciated that specific embodiment described herein is not used to limit this only in order to explain the present invention
Bright.
Embodiment 1
(1) by mixed material（Isosorbide-5-Nitrae-butylene glycol 90 ~ 99%, BDO 0 ~ 9%, Isosorbide-5-Nitrae-butynediols 0 ~ 4%；Propilolic alcohol
0.1 ~ 0.2%, water：0.1~5%）Add in head tank, then pump into through raw material pump and be preheated in preheater 80-120 DEG C, after preheating
Raw material is entered back into, and gained gaseous phase materials are entered in reactor, in catalyst Y type molecular sieve
Under effect, in 150-300 DEG C, through gas and solid phase catalyzing normal pressure or Depressor response to gas phase dihydrofuran and the Synthesis liquid of water, described
Reaction velocity is 0.5-2.5/h, and the vacuum of the Depressor response is 0 ~ 0.08MPa；The Synthesis liquid is consisted of：Dihydrofuran
60~65%（Tetrahydrofuran containing 2,3- and 2,5- tetrahydrofurans）, water 15 ~ 18%, butylene glycol 10 ~ 20%, furan 1 ~ 3%, crotonic aldehyde
0.1 ~ 0.3%, 3- hydroxyl tetrahydrofuran 0.1 ~ 0.5%, butyrolactone 0.1 ~ 0.3%, octenal 0.1 ~ 0.3%；
(2) step (1) gained gas phase dihydrofuran sequentially enters preheater and condenser with the Synthesis liquid of water, is cooled to 20-30
After DEG C, raw material transfer tank is entered, then is delivered in the middle part of first rectifying column through delivery pump I, collected in first rectifying column bottom of towe not anti-
The 1,4- butylene glycols that answers（Content is 85 ~ 95%）, and be back in superheater by delivery pump II, first rectifying column tower top is received
Collection mixing dihydrofuran fraction, and be delivered in the middle part of Second distillation column.The first rectifying column number of theoretical plate sum is 16 ~ 25
Block, wherein, theoretical number of plates of rectifying section is 10 ~ 15 pieces, and profit reduction and reserving section number of theoretical plate is 6 ~ 10 pieces；First rectifying column operating condition is：
0 ~ 0.08MPa of vacuum, 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 furan, purity are 50 ~ 99.5%, produce DHF finished product in the middle part of rectifying column,
Purity 99.5%, bottom of towe produce DHF heavy constituent（Purity 50 ~ 75%）, it is smart that the fraction pumps into the 3rd by delivery pump III
Evaporate in the middle part of tower.Second distillation column is next door rectifying column pattern, and Second distillation column theoretical plate sum is 60 ~ 70 pieces, wherein, rectifying section
15 ~ 20 pieces of number of theoretical plate, profit reduction and reserving section number of theoretical plate are 20 ~ 26 pieces, 35 ~ 40 pieces of partition wall section number of theoretical plate；Second distillation column is grasped
As condition it is：Atmospheric operation, reflux ratio R=30 ~ 60,32 ~ 50 DEG C of tower top temperature produce furan fraction；Temperature ~ 54.5 DEG C in tower,
Extraction 2,3 dihydro furan；66 ~ 75 DEG C of column bottom temperature, produces DHF heavy constituent fraction.
(4) third distillation column bottom of towe produces rectification waste liquid and through follow-up environmental protection treatment, side line by III serialization of delivery pump
Gas phase extracted waste water is through biochemical treatment（Contain crotonic aldehyde 0.01 ~ 0.3%）, the azeotropic mixture of overhead extraction DHF and water（Pure
Degree 96 ~ 99.5%, aqueous 0 ~ 5%）, in the middle part of azeotropic mixture the 4th rectifying column of entrance.Third distillation column number of theoretical plate sum is 30 ~ 40
Block, wherein, theoretical number of plates of rectifying section is 20 ~ 25 pieces, and profit reduction and reserving section number of theoretical plate is 10 ~ 15 pieces, and Second distillation column charging interpolation is helped
Agent, auxiliary agent are sodium hydrosulfite or 2,6- di-tert-butyl-4-methy phenol；Third distillation column operating condition is：Atmospheric operation, reflux ratio
R=1.0 ~ 1.5,65 DEG C of tower top temperature, 102 ~ 170 DEG C of column bottom temperature, 102 ~ 105 DEG C of side take-off temperature.
(5) the 4th rectifying columns adopt extractant Isosorbide-5-Nitrae-butylene glycol extracting rectifying, solvent ratio（Extraction dosage：Inlet amount matter
Amount ratio）0.5~1：1, overhead extraction finished product DHF（Purity 96 ~ 99.5%, aqueous≤0.05%）, bottom of towe produces aqueous
1,4- butylene glycols（0~5%）.4th rectifying column number of theoretical plate sum is 45 ~ 55 pieces, and wherein, rectification clean-up stage number of theoretical plate is 3
~ 5 pieces, 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 is：Normal pressure
Operation, reflux ratio R=1.0 ~ 1.5, solvent is than 0.5 ~ 1；1,66 DEG C of tower top temperature, 150 ~ 170 DEG C of column bottom temperature.
Embodiment 2
Operate identical with embodiment 1, except for the difference that separative element stops using the 4th rectifying column, raw material to be directly entered head tank,
By reacting and separating, extraction in the middle part of Second distillation column obtains DHF, and extraction at the top of third distillation column obtains 2,5-
Dihydrofuran, gained DHF product purity >=99%, water content≤4.5%；Gained 2,5- dihydrofuran product purities
≥96%.
Embodiment 3
Raw material consists of Isosorbide-5-Nitrae-butylene glycol purity >=98.5%, Isosorbide-5-Nitrae-butynediols purity≤1.2%, and BDO purity≤
0.1%, propilolic alcohol 0.1 ~ 0.2%, moisture 0.1 ~ 0.2%
Operated using 1 identical of embodiment, except for the difference that synthesis reactor adopts low-temp reaction, 150 ~ 250 DEG C of reaction temperature to close
Increase into production capacity, in the middle part of Second distillation column, produce finished product DHF, purity >=99.5%, at the top of the 4th rectifying column
Extraction finished product DHF, purity 99.5%, third distillation column side take-off waste water Fructus Crotonis aldehyde≤0.1%, waste water COD
10000 ~ 20000mg/L of value, subsequent wastewater treatment difficulty are reduced.
Embodiment 4
Raw material constitutes situation：Isosorbide-5-Nitrae-butylene glycol purity >=99%, Isosorbide-5-Nitrae-butynediols purity≤0.5%, BDO purity
≤ 2 ~ 3%, propilolic alcohol 0.1 ~ 0.2%, moisture≤0.05%
With embodiment 1, synthesis reactor adopts pyroreaction, 250 ~ 300 DEG C of reaction temperature, synthetically produced ability to increase for operating process
Greatly, finished product DHF is produced in the middle part of Second distillation column, purity >=99.5%, rectifying column are not added with antioxygen auxiliary agent；4th rectification
Top of tower produces finished product DHF, purity 97 ~ 98%, and third distillation column side take-off waste water Fructus Crotonis aldehyde 0.5 ~
1.5%, 50000 ~ 100000mg/L of COD value of waste water, subsequent wastewater treatment difficulty increase；Using high-temperature nuclei dihydrofuran, 2,3-
Dihydrofuran yield increases, and DHF and the reacted ratio of DHF can reach 1：1 ratio
Embodiment described above is one kind preferably scheme of the present invention, not makees any pro forma limit to the present invention
System, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (9)
1. a kind of dihydrofuran be continuously synthesizing to and isomer separation method, it is characterised in that the dihydrofuran serialization
Synthesis is comprised the steps with detached method：
(1) mixed material containing Isosorbide-5-Nitrae-butylene glycol is added in head tank, then pumps in preheater through raw material pump and be preheated to
80-120 DEG C, the raw material after preheating is entered back into, and gained gaseous phase materials are entered in reactor,
Under high-performance solid catalyst action, in 150-300 DEG C, gas phase dihydrofuran is obtained through gas and solid phase catalyzing normal pressure or Depressor response
With the Synthesis liquid of water, the reaction velocity is 0.1-2.5/h, and the vacuum of the Depressor response is 0.01 ~ 0.90MPa；
(2) step (1) gained gas phase dihydrofuran sequentially enters preheater and condenser with the Synthesis liquid of water, is cooled to 20-30
After DEG C, raw material transfer tank is entered, then is delivered in the middle part of first rectifying column through delivery pump I, collected in first rectifying column bottom of towe not anti-
Isosorbide-5-Nitrae-the butylene glycol that answers, and be back in superheater by delivery pump II, first rectifying column overhead collection mixes dihydrofuran
Fraction, and be delivered in the middle part of Second distillation column；
(3) Second distillation column overhead extraction furan, produces DHF finished product in the middle part of rectifying column, bottom of towe produces 2,5- bis-
Hydrogen furan heavy constituent, the fraction are pumped in the middle part of third distillation column by delivery pump III；
(4) third distillation column bottom of towe produces rectification waste liquid and through follow-up environmental protection treatment, side line gas phase by III serialization of delivery pump
Azeotropic mixture of the extracted waste water through biochemical treatment, overhead extraction DHF and water, the azeotropic mixture are entered in the 4th rectifying column
Portion；
(5) the 4th rectifying columns adopt Isosorbide-5-Nitrae-butylene glycol extracting rectifying, overhead extraction finished product DHF, bottom of towe to produce
Aqueous 1,4- butylene glycols.
2. dihydrofuran as claimed in claim 1 be continuously synthesizing to and isomer separation method, it is characterised in that step (1)
Described in mixed material include following parts by weight component：0 ~ 9 part of 90 ~ 99 parts of 1,4- butylene glycols and 1,4- butanediols.
3. dihydrofuran as claimed in claim 1 be continuously synthesizing to and isomer separation method, it is characterised in that step (1)
Described in reactor be tubular fixed-bed catalytic reactor, inside is provided with expansion joint；Solid catalysis are imitated in the built-in raising of reactor
There is gas-solid phase reaction by beds in agent, material.
4. dihydrofuran as described in claim 1 or 3 be continuously synthesizing to and isomer separation method, it is characterised in that step
(1) high-performance solid catalyst described in is support type acid-exchange resin, carried heteropoly acid and Y, β, ZSM -5 types point
Son sieve, support type acid-exchange resin or suported superacid.
5. dihydrofuran as claimed in claim 1 be continuously synthesizing to and isomer separation method, it is characterised in that step (2)
Described in first rectifying column number of theoretical plate sum be 16 ~ 25 pieces, wherein, theoretical number of plates of rectifying section is 10 ~ 15 pieces, and profit reduction and reserving section is theoretical
Plate number is 6 ~ 10 pieces；First rectifying column operating condition is：0 ~ 0.08MPa of vacuum, 5 ~ 75 DEG C of tower top temperature, column bottom temperature 150 ~
240 DEG C, reflux ratio R=0.5 ~ 3.
6. dihydrofuran as claimed in claim 1 be continuously synthesizing to and isomer separation method, it is characterised in that step (3)
Described in Second distillation column be next door rectifying column pattern, Second distillation column theoretical plate sum be 60 ~ 70 pieces, wherein, rectifying section manage
By 15 ~ 20 pieces of plate number, profit reduction and reserving section number of theoretical plate is 20 ~ 26 pieces, 35 ~ 40 pieces of partition wall section number of theoretical plate；Second distillation column is operated
Condition is：Atmospheric operation, reflux ratio R=30 ~ 60,32 ~ 50 DEG C of tower top temperature produce furan fraction；0 ~ 54.5 DEG C of temperature in tower,
Extraction 2,3 dihydro furan；66 ~ 75 DEG C of column bottom temperature, produces DHF heavy constituent fraction.
7. dihydrofuran as claimed in claim 1 be continuously synthesizing to and isomer separation method, it is characterised in that step (4)
Described in third distillation column number of theoretical plate sum be 30 ~ 40 pieces, wherein, theoretical number of plates of rectifying section is 20 ~ 25 pieces, and profit reduction and reserving section is theoretical
Plate number is 10 ~ 15 pieces, and auxiliary agent is added in Second distillation column charging, and auxiliary agent mainly suppresses dihydrofuran peroxide to generate, and prevents
Peroxide accumulation and occur explosion danger, auxiliary agent be sodium hydrosulfite or 2,6- di-tert-butyl-4-methy phenols；Third distillation column is grasped
As condition it is：Atmospheric 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℃.
8. dihydrofuran as claimed in claim 1 be continuously synthesizing to and isomer separation method, it is characterised in that step (5)
Described in the 4th rectifying column number of theoretical plate sum be 45 ~ 55 pieces, wherein, rectification clean-up stage number of theoretical plate be 0 ~ 5 piece, extraction section manage
It is 25 ~ 30 pieces by plate number, 15 ~ 20 pieces of stripping section number of theoretical plate；4th rectifying column operating condition is：Atmospheric operation, reflux ratio R=
1.0 ~ 1.5, solvent is than 0.5 ~ 1；1,66 DEG C of tower top temperature, 150 ~ 170 DEG C of column bottom temperature.
9. dihydrofuran as claimed in claim 1 be continuously synthesizing to and isomer separation method, it is characterised in that described first
Rectifying column is serialization rectifying column, and Second distillation column is divided-wall distillation column, and third distillation column is serialization rectifying column, and the 4th is smart
Tower is evaporated for extracting rectifying tower, tower bottom reboiler is heated using pump forced circulation, overhead condenser adopts recirculated water and cold
Freeze the cooling of water twin-stage.
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| CN108191796A (en) * | 2017-12-15 | 2018-06-22 | 浙江先锋科技股份有限公司 | A kind of preparation method of 2,5-dihydrofuran |
| 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 |
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| CN108191796A (en) * | 2017-12-15 | 2018-06-22 | 浙江先锋科技股份有限公司 | A kind of preparation method of 2,5-dihydrofuran |
| CN108191796B (en) * | 2017-12-15 | 2019-11-19 | 浙江先锋科技股份有限公司 | A kind of preparation method of 2,5-dihydrofuran |
| 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 |
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