CN105622549B - A kind of method that the catalysis of modified Nano gama-alumina prepares high-purity tetrahydrofuran - Google Patents
A kind of method that the catalysis of modified Nano gama-alumina prepares high-purity tetrahydrofuran Download PDFInfo
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Abstract
The invention discloses pass through a kind of method for preparing high-purity tetrahydrofuran (THF) using modified Nano gamma-alumina catalyst, this method is specifically under normal pressure, using modified Nano gama-alumina as catalyst, 1,4-butanediol dehydration ring closure successive reaction is prepared into high-purity tetrahydrofuran.The modified nano-alumina is gama-alumina particulate load magnesium metal or potassium, sodium etc., and load capacity is 0.1~15 wt%, and reaction temperature is 150~350oC; the method that the present invention prepares high-purity tetrahydrofuran by modified Nano gamma-alumina catalyst can react in atmospheric conditions, not need solvent or inert gas shielding; reaction temperature 150-350 degree; to technical process require it is lower, cost is relatively low, by-product is few, reaction yield height (> 85%); (> 99%) with high purity; reaction is continuous, easy to operate, is easy to industrialized implementation.
Description
Technical field
The invention belongs to chemical technology fields, and it is high to relate more specifically to a kind of modified Nano gamma-alumina catalyst preparation
The method of purity tetrahydrofuran.
Background technique
Tetrahydrofuran is pentacyclic Oxygenic heterocyclic compounds, is a kind of important widely used Organic Chemicals, by
It is widely used in surface coating, anticorrosive paint usually as fine solvent in the property with highly polar, low boiling point, hypotoxicity
With the preparation of film coating, and it is applied in the organic chemical reactions such as polymerization reaction, esterification.Tetrahydrofuran it is another heavy
Want purposes be for produce polytetramethylene ether diol (PTMEG) and manufacture polyurethane elastomeric fiber (Spandex), elastomer and
Poly- aminoacyl artificial leather etc..In addition tetrahydrofuran is also widely used in medical industry and accurate tape industry.
Currently, the industrialized preparing process of tetrahydrofuran mainly uses 1,4-butanediol catalytic dehydration to be cyclized method.Preparation
Tetrahydrofuran need to obtain Isosorbide-5-Nitrae-butanediol further cyclodehydration tetrahydrofuran (THF), and the dehydration of Isosorbide-5-Nitrae-butanediol passes through
Two steps are implemented, the two steps include: that (1) in the presence of acidic catalysts closes Isosorbide-5-Nitrae-butanediol reaction dehydration
Ring, (2) then remove water from aqueous reaction product.The yield of this method depends on acidic catalyst used in reaction process
The performance of agent, it is therefore desirable to be studied all the time to develop for Isosorbide-5-Nitrae-Butanediol effective catalyst.
The cyclodehydration of Isosorbide-5-Nitrae-butanediol generally uses acidic catalyst, it is known that Isosorbide-5-Nitrae-Butanediol prepare tetrahydro
The catalyst of furans has sulfuric acid and gama-alumina, η-type aluminium oxide.Such as: United States Patent (USP) US 4665205, which is disclosed, to be used
Make the method for 1,4-Butanediols under conditions of inorganic acids catalyst (such as sulfuric acid).However, the corrosivity due to sulfuric acid is endangered
Danger exists, then needs special anti-sour equipment, provides the skill of equipment and increases, the serious pollution environment such as spent acid of generation, and
Coke-like substance can be also generated in reaction process, greatly increase the complexity of reaction process.
Patent SU1158562, which is disclosed, reports one kind 320oC, under condition of normal pressure, with gama-alumina or containing the γ-of chlorine
Aluminium oxide is the method for preparing tetrahydrofuran of catalyst.When the liquid hourly space velocity (LHSV) of 1,4-butanediols is 7.0 h-1When, Isosorbide-5-Nitrae-fourth
The conversion ratio of glycol is 100%, and the selectivity of tetrahydrofuran is 100%, and when Isosorbide-5-Nitrae-butanediol liquid hourly space velocity (LHSV) is improved to 7.5
h-1When, Isosorbide-5-Nitrae-butanediol conversion ratio drops to 97.4%, and the selectivity of tetrahydrofuran drops to 93.6%.SU1294805 report
A kind of preparation method of tetrahydrofuran in road is the silicon for being respectively 16.l nm, 35.4 nm, 70 nm different pore sizes with average pore size
Glue is as catalyst, before use, catalyst is needing under an inert atmosphere 400~420oC activates 30~45 min, and use is above-mentioned
Catalyst is in normal pressure 420oC, volume space velocity is 38 g/cm when liquid3.It is reacted under the reaction condition of h, Isosorbide-5-Nitrae-butanediol
Conversion ratio 100%, tetrahydrofuran are selectively 99.2%；And at that same temperature, when liquid hourly space velocity (LHSV) increases to 61.5 g/cm3.h
When, Isosorbide-5-Nitrae-butanediol conversion ratio drops to 89.3 %, and the selectivity of tetrahydrofuran is reduced to 99.3%.
In addition, there are also several sides for producing tetrahydrofuran in the presence of different acidic catalysts by Isosorbide-5-Nitrae-butanediol
Method, for example, United States Patent (USP) US6204399, Japanese Unexamined Patent Application Publication No. Hei 09-059191, United States Patent (USP)
US4136099 and Japanese Unexamined Patent Application Publication No. Sho 61-126080 are disclosed and are urged respectively using aluminium oxide
1,4-the butanediols carried out under conditions of agent, silica-alumina catalyst, alumina load tungsten oxide catalyst and heteropolyacid catalyst
Dehydration.However, these methods still relate to the shortcomings that catalyst activity and stability.In short, existing Isosorbide-5-Nitrae-butanediol
The method that cyclodehydration produces tetrahydrofuran haves the defects that reaction temperature is excessively high, catalyst treatment ability is low, at raising
Reason ability, then raw material Isosorbide-5-Nitrae-butanediol conversion ratio can be decreased obviously.
Summary of the invention
1, the purpose of the present invention.
Invention is designed to provide a kind of method with modified nano-alumina catalyst preparation high-purity tetrahydrofuran,
The problem that this method solve reaction temperatures in the prior art is excessively high, catalyst treatment ability is low, improves the condition of processing capacity
The conversion ratio of 1,4-butanediol of lower raw material can't decline.
2, the technical solution adopted in the present invention.
The method of modified nano-alumina catalyst preparation high-purity tetrahydrofuran, under normal pressure, in modified Nano γ-oxygen
Isosorbide-5-Nitrae-Butanediol cyclization reaction, preparation step are carried out under the action of change Al catalysts are as follows:
(1) modified modified Nano gamma-alumina catalyst is added in the reactor, Isosorbide-5-Nitrae-butanediol is added, 150
~350oIt is reacted at a temperature of C, steams reaction product tetrahydrofuran after condenser condenses again through fraction water device water-dividing, obtain tetrahydro
Furans crude product；
(2) tetrahydrofuran crude product is dry by drying tower, drying temperature 20~30oC ；Into rectifying column rectifying, rectifying
Column overhead operating pressure is normal pressure, rectifying tower top operation temperature 65~66oC；
(3) it is condensed again through condenser, removes a small amount of by-product, obtain the tetrahydrofuran product that purity is 99% or more.
In further specific embodiment, changing for powder is added in the step (1) in tank reactor (A1)
Property nanometer gamma-alumina catalyst.
In further specific embodiment, in the step (1) in fixed bed tower reactor (B2), it is added solid
The modified Nano gama-alumina particle of body, Isosorbide-5-Nitrae-butanediol are pre-processed by preheater (B1), and pretreated activation temperature is
150~200oC。
In further specific embodiment, in the step (1) in fixed bed tower reactor (B2), it is added solid
The modified Nano gama-alumina particle of body, Isosorbide-5-Nitrae-butanediol are pre-processed by preheater (B1), and heater outlet temperature is kept
170 oC, temperature of reactor maintain 200oC, successive reaction 100 hours.
In further specific embodiment, modified nano-alumina (10~100 nm of particle diameter), carried metal can
Think one or more of metals such as potassium, calcium, sodium, zirconium, molybdenum, nickel, tungsten, magnesium, copper.Carried metal content: the wt% of 0.1 %~15.
In further specific embodiment, modified nano-alumina the preparation method comprises the following steps: by industrial goods nanometer gamma oxidation
Aluminium is added in the precursor solution of 0.1~15 wt% carried metal of concentration, is stored at room temperature 24 h, vacuum condition (2.0~
2.5 kPa) under rotary evaporation obtain solid, spheroiding, cylindrical type or trifolium-shaped are squeezed, 100~130oIt is dry under C
1~5 h, temperature programming is in Muffle kiln roasting: 450oC roast 1~3 h, 500oC roast 1 h, 550oC roasts 4 h, cold
But to room temperature to get arrive modified Nano gamma-alumina catalyst.
In further specific embodiment, the use for catalyst, in fixed bed tower reactor B2, according to tool
Reactor according is preferably sized to reactor diameter: catalyst particle size=5~10, reactor length: catalyst particle size=50~
100。
In further specific embodiment, the water removal sections of the reaction system first pass through water segregator and carry out oil reservoir water layer
Separation after, oil reservoir enters that drying tower is dry, and desiccant is the molecular sieve of recyclable regenerative, preferably 4A molecular sieve.
In further specific embodiment, the rectifying column of purifying products part is packed tower, and filler is using general
Efficient regular screen waviness packings.
In further specific embodiment, which is synthesis under normal pressure, is not required to that any solvent is added, is also not required in reaction
Carry out the inert gas shieldings such as nitrogen or helium.
The method according to the invention, reaction temperature are 150~350oC, preferred range are 170~270oC。
3, beneficial effects of the present invention.
The method that the present invention prepares high-purity tetrahydrofuran by modified Nano gamma-alumina catalyst, in condition of normal pressure
Under can react, do not need solvent or inert gas shielding, reaction temperature 150-350 degree, to technical process require it is lower,
Cost is relatively low, and by-product is few, and reaction yield height (> 85%), (> 99%) with high purity, reaction is continuous, easy to operate, is easy to work
The implementation of industry.
Detailed description of the invention
Fig. 1 is the atmospheric kettle according to the present invention by the method for 1,4-Butanediol next life producing tetrahydrofurans (THF)
Formula reaction process flow chart.
In Fig. 1, A1 reactor, A2 condenser, A3 water segregator, A4 drying tower, A5 rectifying column, A6 condenser.
Fig. 2 is the fixed bed tower according to the present invention by the method for 1,4-Butanediol next life producing tetrahydrofurans (THF)
Formula process flow chart.
In Fig. 2, B1 preheater, B2 fixed bed reactors, B3 condenser, B4 water segregator, B5 drying tower, B6 rectifying column, B7
Condenser.
Specific embodiment
In order to enable the auditor especially public of Patent Office that technical spirit of the invention is more clearly understood and have
Beneficial effect, applicant will elaborate by way of examples below, but be not to this hair to the description of embodiment
The limitation of bright scheme, the made only formal but not substantive equivalent transformation of any design according to the present invention are all answered
It is considered as technical solution of the present invention scope.
Embodiment
Reactor of the invention can be fixed bed reactors or mixing reactor, such as use Liquid-phase reactor, gas
Phase reaction device, tank reactor, fixed bed tower reactor are implemented.Pretreated activation temperature is 150~200oC, reaction
The reaction temperature of device is 200~300oC.Successively using including containing one or more modified Nano gamma-alumina catalyst beds
Dehydration ring closure area, the product recovery section of destilling tower, high boiling product removal area and charging derive from product recovery section bottoms
Device needed for THF group assigns to isomerization zone.
In embodiments of the invention, it is preferable to use 0.1~15 for the process muttered of being creaked by Isosorbide-5-Nitrae-butanediol production tetrahydro
The modified nano-alumina catalyst of wt%.If the dosage of modified nano-alumina catalyst is lower than 0.1 wt%, catalyst
Dosage it is insufficient, will lead to reaction efficiency reduction.On the other hand, if the dosage of modified nano-alumina catalyst is higher than 15
Wt%, then catalyst excess, will cause the waste of catalyst.
The production method of tetrahydrofuran according to embodiments of the present invention is not particularly limited.It can be by side as described below
Method prepares tetrahydrofuran.
Embodiment 1
As shown in Figure 1, the preparation method of high-purity tetrahydrofuran provided by the invention, under normal pressure by Isosorbide-5-Nitrae-butanediol
The method of dehydration ring closure reaction, comprising the following steps:
(1) the modified Nano gamma-alumina catalyst of powder is added in tank reactor A1, Isosorbide-5-Nitrae-butanediol is added,
150~350oIt is reacted at a temperature of C, steams reaction product tetrahydrofuran after condenser A2 condensation again through water segregator A3 points
Water obtains tetrahydrofuran crude product, and purity is 95% or so；
(2) tetrahydrofuran crude product is dry by drying tower A4, drying temperature 20~30oC ；Enter back into rectifying column A5 essence
It evaporates, the top of the distillation column operating pressure is normal pressure, rectifying tower top operation temperature 65~66oC；
(3) it is condensed again through condenser A6, removes a small amount of by-product, obtained the tetrahydrofuran that purity is 99% or more and produce
Product；
It removes a small amount of by-product: specifically including that then 2,3-dihydrofuran, tetrahydrofuran obtain high-purity tetrahydro furan
It mutters.
Embodiment 2
As shown in Fig. 2, the preparation method of high-purity tetrahydrofuran provided by the invention, under normal pressure by Isosorbide-5-Nitrae-butanediol
The method of dehydration ring closure reaction, comprising the following steps:
(1) in fixed bed tower reactor B2, the modified Nano gama-alumina particle of solid, Isosorbide-5-Nitrae-butanediol warp is added
Preheater B1 pretreatment is crossed, heater outlet temperature keeps 170oC, temperature of reactor maintain 200oC, successive reaction 100 hours；
(2) preheating Isosorbide-5-Nitrae-butanediol is continuously added in reactor B 2, reaction temperature maintains 150~350oC, preferably
200 oC, reaction product are condensed through condenser B3, and after water segregator B4 divides water, obtain the tetrahydrofuran crude product that purity is 95%；
(3) tetrahydrofuran crude product is dry by drying tower B5, condenses into rectifying column B6 rectifying, condenser B7, obtains 99%
The above product, drying temperature 20~30oC, the top of the distillation column operating pressure are normal pressure, rectifying tower top operation temperature 65~66oC。
In above 2 kinds of the embodiment, raw material Isosorbide-5-Nitrae-butanediol is industrial goods, 99.1 % of content (GC), moisture 0.2%
(KF).Select industrial goods γ-phase nano aluminium oxide, 20 nm of particle diameter, as catalyst A.
Reaction temperature is preferably 150oC to 350oC, and more preferably 170oC to 270oC.In above-mentioned temperature range
Interior reaction efficiency is higher.Temperature is lower than 150oIt is poor that C will lead to reaction efficiency, and temperature is higher than 350oC can cause tetrahydrofuran
Thermal decomposition, so that selectivity can be reduced.
In the methods of the invention, the composition of raw material and product is with gas chromatographic detection (GC):
It selects DB-5MS capillary column (mm × 0. 25 of 30 m × 0. 25 um), in Agilent5975 gas chromatograph
Upper analysis, hydrogen flame ionization detector.Testing conditions: initial temperature 50oC, 10oC/min temperature programming: final temperature 200oC maintains 5min.Injector temperature: 180oC, detector temperature: 220oC。
In the present invention, the detection method of moisture is Karl_Fischer method (KF) in stock Product.
Reaction yield is calculated according to following formula in the embodiment of the present invention:
Yield=reaction product tetrahydrofuran amount (mol)/1,4-butanediol of raw material amount (mol) × 100 %
Experimental verification:
Method for preparing catalyst 1
The gama-alumina of 20 g is taken to be placed in 250 mL single-necked flasks, it is that 10 wt% magnesium nitrates are molten that concentration, which is then added,
Liquid 80g is stored at room temperature 20 h.(2.0~2.5 kPa) rotary evaporation obtains solid under vacuum condition, is squeezed into cloverleaf pattern
Shape, 110oDry 1 h under C, temperature programming is in Muffle kiln roasting: 450oC roast 1 h, 500oC roast 1 h, 550oC
Roast 4 h.Catalyst A is obtained, being detected magnesium-supported amount is 0.8 wt%.
Method for preparing catalyst 2
It takes the gama-alumina of 20 g to be placed in 250 mL single-necked flasks, 8 wt% potassium nitrate solutions of concentration is then added
50 g are stored at room temperature 20 h.Rotary evaporation obtains solid under vacuum condition (2.0~2.5 kPa), is squeezed into cylindrical shape,
110 oDry 1 h under C, temperature programming is in Muffle kiln roasting: 450oC roast 1 h, 500oC roast 1 h, 550oC roasting
Burn 4 h.Catalyst B is obtained, is 2. 2 wt% through detection potassium load capacity.
Prepare tetrahydrofuran experiment 1
It is that the 1,4-butanediol of 40 g, heating is added in 250 mL reactor bottles that diameter, which is added, in 3 g gama-aluminas
Start to reaction, there is gas generation, starts that raw material 1,4-butanediol is added dropwise, while constantly steaming reaction product, successive reaction 100
H collects product, and after carrying out water removal drying, rectifying obtains product, calculates through detection: product purity 95.0%(GC), moisture 0.08%
(KF), yield is 91 %.
Prepare tetrahydrofuran experiment 2
20 g catalyst A are added in the shell and tube reactor that diameter is a length of 400 mm of 8 mm, start nitrogen purging
3 h start 1,4-butanediol liquid input reactor with metering pump with the speed of 5 mL/min, and heater outlet temperature is protected
Hold 160oC, temperature of reactor maintain 170oC, 100 h of successive reaction collect product, and after carrying out water removal drying, rectifying is produced
Product are calculated through detection: product purity 99.5%(GC), moisture 0.10% (KF), yield 95%.
Prepare tetrahydrofuran experiment 3
20 g catalyst B are added in the shell and tube reactor that diameter is a length of 400 mm of 8 mm, start nitrogen and blow
3 h are swept, are started 1,4-butanediol liquid input reactor, heater outlet temperature with metering pump with the speed of 5 mL/min
Keep 160 oC, temperature of reactor maintenance 170oC, 100 h of successive reaction collect product, and after carrying out water removal drying, rectifying is obtained
Product calculates: product purity 99.3% (GC), moisture 0. 08% (KF), yield 92% through detection.
Prepare tetrahydrofuran experiment 4
With tetrahydrofuran experiment 2 is prepared, selecting gama-alumina is that catalyst reacts in shell and tube reactor, and gained produces
Product purity 93.8% (GC), 0.11 % of moisture (KF), yield 89%.
Table one:
| 1 | 2 | 3 | |
| Catalyst | Magnesium-gama-alumina | Potassium-gama-alumina | Gama-alumina |
| Reaction yield | 95% | 92% | 89% |
As shown in Table 1 as can be seen that the obtained reaction of reaction for using modified nano-alumina particle as catalyst
Yield is obviously high.Therefore, it is produced using the high yield that tetrahydrofuran may be implemented in modified nano-alumina particle.
From described above it is readily apparent that production method according to embodiments of the present invention, the use of modified catalyst
The high yield production of tetrahydrofuran can be realized by simple and low risk production technology, while being solved and being produced
The problem of reaction yield is lower when tetrahydrofuran and potential danger may occur in process of production.
Claims (8)
1. a kind of method of modified nano-alumina catalyst preparation high-purity tetrahydrofuran, under normal pressure, in modified Nano γ-
Isosorbide-5-Nitrae-Butanediol cyclization reaction is carried out under the action of aluminium oxide catalyst, it is characterised in that preparation step are as follows:
(1) modified modified Nano gamma-alumina catalyst is added in the reactor, Isosorbide-5-Nitrae-butanediol is added, 150~350oC
At a temperature of react, steam reaction product tetrahydrofuran after condenser condenses again through fraction water device water-dividing, obtain tetrahydrofuran crude product；
The modified Nano gama-alumina the preparation method comprises the following steps: nanometer gama-alumina is added to the 0.1~15 of concentration
It in the precursor solution of wt% carried metal, is stored at room temperature 24 hours, rotary evaporation obtains under 2.0~2.5 kPa of vacuum condition
Solid squeezes balling-up sheet, cylindric or graininess, 100~130o1~5 hour dry under C, temperature programming is in horse
Not kiln roasting: 450oC roast 1~3 h, 500oC roast 1 h, 550oC roasts 4 h, is cooled to room temperature to get modification is arrived
Nano aluminium oxide；
(2) tetrahydrofuran crude product is dry by drying tower, drying temperature 20~30oC ；Into rectifying column rectifying, the top of the distillation column
Operating pressure is normal pressure, rectifying tower top operation temperature 65~66oC；
(3) it is condensed again through condenser, removes a small amount of by-product, obtain the tetrahydrofuran product that purity is 99% or more.
2. the method for modified nano-alumina catalyst preparation high-purity tetrahydrofuran as described in claim 1, feature exist
In: the preparation of tetrahydrofuran crude product in the step (1): in fixed bed tower reactor (B2), the modified Nano of solid is added
Gama-alumina particle, Isosorbide-5-Nitrae-butanediol are pre-processed by preheater (B1), and pretreated activation temperature is 150~200oC。
3. the method for modified nano-alumina catalyst preparation high-purity tetrahydrofuran as described in claim 1, feature exist
In:
The preparation of tetrahydrofuran crude product in the step (1): using in fixed bed tower reactor (B2), changing for solid is added
Property nanometer gama-alumina particle, Isosorbide-5-Nitrae-butanediol by preheater (B1) pre-process, heater outlet temperature keep 170oC,
Temperature of reactor maintains 200oC, successive reaction 100 hours.
4. the method for modified nano-alumina catalyst preparation high-purity tetrahydrofuran as described in claim 1, feature exist
It is gama-alumina particulate load potassium in described modified Nano gama-alumina, calcium, sodium, zirconium, molybdenum, nickel, tungsten, magnesium is a kind of in copper
Or several metals, load capacity: 0.1~15 wt%.
5. the method for modified nano-alumina catalyst preparation high-purity tetrahydrofuran as described in claim 1, feature exist
In: in fixed bed tower reactor, reactor diameter: catalyst particle size=5~10, reactor length: catalyst particle size=
50~100.
6. the method for the modified nano-alumina catalyst preparation high-purity tetrahydrofuran as described in claim 1, feature exist
In: 4A molecular sieve is filled in drying tower.
7. the method for modified nano-alumina catalyst preparation high-purity tetrahydrofuran as described in claim 1, feature exist
In: rectifying column is using efficient regular screen waviness packings.
8. the method for modified nano-alumina catalyst preparation high-purity tetrahydrofuran as described in claim 1, feature exist
In: reaction temperature is 170~270oC。
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