CN105622549A - Method for preparing high-purity tetrahydrofuran by using modified nano gamma-alumina catalyst - Google Patents
Method for preparing high-purity tetrahydrofuran by using modified nano gamma-alumina catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity tetrahydrofuran (THF) by using modified nano gamma-alumina catalyst. The method specifically comprises the steps: at atmospheric pressure and with the modified nano gamma-alumina as the catalyst, carrying out dehydration ring-closing continuous reaction of 1,4-butanediol to prepare the high-purity tetrahydrofuran. The modified nano alumina is formed by loading gamma-alumina particles with metal magnesium or potassium or sodium and the like, the loading amount is 0.1-15 wt%, and the reaction temperature is 150-350 DEG C; according to the method for preparing the high-purity tetrahydrofuran by using the modified nano gamma-alumina catalyst, the reaction can be carried out under the condition of atmospheric pressure, no solvent or inert gas protection is required, the reaction temperature is 150-350 DEG C, the requirements on the technological process are relatively low, the cost is relatively low, fewer by-products are produced, the receivable rate is high (more than 85%), the purity is high (more than 99%), the reaction is continuous, the operation is simple and industrialized implementation is easy to achieve.
Description
Technical field
The invention belongs to chemical technology field, relate more specifically to a kind of modified Nano��-Aluminium oxide catalyst prepares the method for high-purity tetrahydrofuran.
Background technology
Oxolane is pentacyclic Oxygenic heterocyclic compounds, it it is a kind of important Organic Chemicals of many uses, owing to having highly polar, low boiling, hypotoxic character, usually used as fine solvent, it is widely used in the preparation of surface coating, anticorrosive paint and film coating, and is applied in the organic chemical reactions such as polyreaction, esterification. Another important use of oxolane is for producing polytetramethylene ether diol (PTMEG) and manufacturing polyurethane elastomeric fiber (Spandex), elastomer and poly-aminoacyl artificial leather etc. Additionally in medical industry and accurate tape industry, oxolane is also widely used.
At present, the industrialized preparing process of oxolane mainly adopts BDO catalytic dehydration cyclisation method. Prepare oxolane, need to by 1, the further cyclodehydration of 4-butanediol obtains oxolane (THF), 1, the dehydration of 4-butanediol is implemented by two steps, the two step includes: (1) makes BDO reaction dehydration ring closure under the existence of acidic catalyst, and (2) then remove water from moisture product. The yield of the method depends on the performance of acidic catalyst used in course of reaction, it is therefore desirable to carry out all the time studying to develop the effective catalyst for BDO dehydration.
The cyclodehydration of BDO is generally adopted acidic catalyst, it is known that BDO Dehydration have sulphuric acid and �� for the catalyst of oxolane-Aluminium oxide, ��-Type aluminium oxide. Such as: US Patent No. 4665205 discloses the method making 1,4-Butanediol when using inorganic acids catalyst (such as sulphuric acid). But, owing to the corrosivity danger of sulphuric acid exists, then need special anti-sour equipment, the serious environment pollutions such as making the skill of equipment provide increases, the spent acid of generation, and course of reaction also can produce coke-like material, greatly increase the complexity of reaction process.
Patent SU1158562 openly reports a kind of 320oUnder C, condition of normal pressure, with��-Aluminium oxide or chloride ��-Aluminium oxide is the method preparing oxolane of catalyst. When the liquid hourly space velocity (LHSV) of 1,4-butanediol is 7.0h-1Time, the conversion ratio of BDO is 100%, and the selectivity of oxolane is 100%, and when the liquid hourly space velocity (LHSV) of BDO is increased to 7.5h-1Time, the conversion ratio of BDO drops to 97.4%, and the selectivity of oxolane drops to 93.6%. The preparation method that SU1294805 reports a kind of oxolane, is using the silica gel of average pore size respectively 16.lnm, 35.4nm, 70nm different pore size as catalyst, and before using, catalyst is needing under an inert atmosphere 400��420oC activates 30��45min, adopts above-mentioned catalyst at normal pressure 420oC, during liquid, volume space velocity is 38g/cm3.Reacting under the reaction condition of h, the conversion ratio 100% of BDO, oxolane selectivity is 99.2%; And at that same temperature, when liquid hourly space velocity (LHSV) increases to 61.5g/cm3.During h, the conversion ratio of BDO drops to 89.3%, and the selectivity of oxolane reduces to 99.3%.
Additionally, also have several by 1,4-butanediol produces the method for oxolane under the existence of different acidic catalysts, such as, US Patent No. 6204399, Japanese Unexamined Patent Application Publication No.Hei09-059191, US Patent No. 4136099 and Japanese Unexamined Patent Application Publication No.Sho61-126080 disclose the BDO dehydration carried out respectively when using aluminium oxide catalyst, silica-alumina catalyst, alumina load tungsten oxide catalyst and heteropolyacid catalyst. But, these methods still have the shortcoming relating to catalyst activity and stability. In a word, existing BDO cyclodehydration is produced the method for oxolane and all be there is the defect that reaction temperature is too high, catalyst treatment ability is low, and as improved disposal ability, then the conversion ratio of raw material BDO can be decreased obviously.
Summary of the invention
1, the purpose of the present invention.
A kind of method that the purpose of invention is in that to provide modified nano-alumina catalyst preparing high-purity tetrahydrofuran, this method solve the problem that reaction temperature in prior art is too high, catalyst treatment ability is low, improve the conversion ratio of raw material BDO when disposal ability can't decline.
2, the technical solution adopted in the present invention.
The method of modified nano-alumina catalyst preparing high-purity tetrahydrofuran, at ambient pressure, at modified Nano��-Carrying out the reaction of BDO dehydration ring closure under the effect of aluminium oxide catalyst, preparation process is:
(1) modified modified Nano is added in the reactor��-Aluminium oxide catalyst, adds BDO, 150��350oReact at C temperature, steam after the condensed device of product oxolane condenses then through fraction water device water-dividing, obtain oxolane crude product;
(2) oxolane crude product dries through drying tower, baking temperature 20��30oC; Entering rectifying column rectification, rectifying column tower top operation pressure is normal pressure, rectifying tower top operation temperature 65��66oC;
(3) condense then through condenser, remove a small amount of by-product, obtain the oxolane product that purity is more than 99%.
Further in specific embodiment, described step (1) adds in tank reactor (A1) modified Nano of powder��-Aluminium oxide catalyst.
Further in specific embodiment, in described step (1) in fixing bed tower reactor (B2), add the modified Nano of solid��-Alumina particle, BDO is through preheater (B1) pretreatment, and the activation temperature of pretreatment is 150��200oC��
Further in specific embodiment, in described step (1) in fixing bed tower reactor (B2), add the modified Nano of solid��-Alumina particle, BDO is through preheater (B1) pretreatment, and heater outlet temperature keeps 170oC, temperature of reactor maintains 200oC, successive reaction 100 hours.
Further in specific embodiment, modified nano-alumina (particle diameter 10��100nm), carried metal can be one or more metals such as potassium, calcium, sodium, zirconium, molybdenum, nickel, tungsten, magnesium, copper. Carried metal content: 0.1%��15wt%.
Further in specific embodiment, the preparation method of modified nano-alumina is: by industrial goods nanometer��-Aluminium oxide joins in the precursor solution of 0.1��15wt% carried metal of concentration, and room temperature stands 24h, and under vacuum condition (2.0��2.5kPa), rotary evaporation obtains solid, is squeezed into ball-type, column type or trifolium-shaped, 100��130oDry 1��5h under C, temperature programming is roasting in Muffle furnace: 450oC roasting 1��3h, 500oC roasting 1h, 550oC roasting 4h, is cooled to room temperature, namely obtains modified Nano��-Aluminium oxide catalyst.
Further in specific embodiment, for the use of catalyst, in fixing bed tower reactor B2, it is preferably sized to reactor diameter according to specific reactor: catalyst particle size=5��10, reactor length: catalyst particle size=50��100.
Further in specific embodiment, the water removal sections of this reaction system, after first passing through the separation that water knockout drum carries out oil reservoir water layer, oil reservoir enters drying tower and dries, and desiccant is the molecular sieve of recyclable regenerative, it is preferable that 4A molecular sieve.
Further in specific embodiment, the rectifying column of purifying products part is packed tower, and its filler is adopt general efficient structured wire corrugated wire gauze packing.
Further in specific embodiment, this reaction is synthesis under normal pressure, does not need to add any solvent, does not also need to carry out the inert gas shielding such as nitrogen or helium in reaction.
According to the method for the present invention, reaction temperature is 150��350oC, it is preferred that scope is 170��270oC��
3, beneficial effects of the present invention.
The present invention passes through modified Nano��-Aluminium oxide catalyst prepares the method for high-purity tetrahydrofuran; can react in atmospheric conditions; do not need solvent or inert gas shielding, reaction temperature 150-350 degree, technical process is required relatively low, less costly; by-product is few; high (> 85% of reaction yield), high (> 99% of purity), reaction is continuously; simple to operate, it is easy to industrialized enforcement.
Accompanying drawing explanation
Fig. 1 is the normal pressure autoclave reaction process flow chart of the method passing through 1,4-Butanediol producing tetrahydrofuran in next life (THF) according to the present invention.
In Fig. 1, A1 reactor, A2 condenser, A3 water knockout drum, A4 drying tower, A5 rectifying column, A6 condenser.
Fig. 2 is the tower process chart of fixing bed of the method passing through 1,4-Butanediol producing tetrahydrofuran in next life (THF) according to the present invention.
In Fig. 2, B1 preheater, B2 fixed bed reactors, B3 condenser, B4 water knockout drum, B5 drying tower, B6 rectifying column, B7 condenser.
Detailed description of the invention
In order to enable the auditor especially public of Patent Office to be more clearly understood from technical spirit and the beneficial effect of the present invention, applicant will elaborate below by way of example, but the description to embodiment is not all the restriction to the present invention program, any foundation pro forma but not substantial equivalent transformation that is only done by present inventive concept is regarded as technical scheme category.
Embodiment
The reactor of the present invention can be fixed bed reactors or mixing reactor, for instance uses Liquid-phase reactor, Gas-phase reactor, tank reactor, fixing bed tower reactor to implement. The activation temperature of pretreatment is 150��200oC, the reaction temperature of reactor is 200��300oC. Utilize successively and include containing one or more modified Nanos��-The dehydration ring closure district of aluminium oxide catalyst bed, the product recovery section of distillation column, high boiling product are removed district and charging and are derived from the THF component of product recovery section bottoms to the device needed for isomerization zone.
In embodiments of the invention, BDO production tetrahydrochysene the process creakily muttered is preferably used the modified nano-alumina catalyst of 0.1��15wt%. If the consumption of modified nano-alumina catalyst is lower than 0.1wt%, then the consumption of catalyst is not enough, can cause that reaction efficiency reduces. On the other hand, if the consumption of modified nano-alumina catalyst is higher than 15wt%, then catalyst excess, the waste of catalyst can be caused.
The production method of oxolane according to embodiments of the present invention is not particularly limited. Oxolane can be prepared by method described below.
Embodiment 1
As it is shown in figure 1, the preparation method of high-purity tetrahydrofuran provided by the invention, the method at ambient pressure BDO dehydration ring closure reacted, comprise the following steps:
(1) in tank reactor A1, add the modified Nano of powder��-Aluminium oxide catalyst, adds BDO, 150��350oReacting at C temperature, divide water then through water knockout drum A3, obtain oxolane crude product after steaming the condensed device A2 condensation of product oxolane, purity is about 95%;
(2) oxolane crude product dries through drying tower A4, baking temperature 20��30oC; Entering back into rectifying column A5 rectification, rectifying column tower top operation pressure is normal pressure, rectifying tower top operation temperature 65��66oC;
(3) condense then through condenser A6, remove a small amount of by-product, obtain the oxolane product that purity is more than 99%;
Remove a small amount of by-product: specifically include that DHF, oxolane, then obtain high-purity tetrahydrofuran.
Embodiment 2
As in figure 2 it is shown, the preparation method of high-purity tetrahydrofuran provided by the invention, the method at ambient pressure BDO dehydration ring closure reacted, comprise the following steps:
(1) in fixing bed tower reactor B2, the modified Nano of solid is added��-Alumina particle, BDO is through preheater B1 pretreatment, and heater outlet temperature keeps 170oC, temperature of reactor maintains 200oC, successive reaction 100 hours;
(2) being continuously added in reactor B 2 by preheating BDO, reaction temperature maintains 150��350oC, it is preferable that 200oC, the condensed device B3 condensation of product, and after water knockout drum B4 divides water, obtain the oxolane crude product that purity is 95%;
(3) oxolane crude product dries through drying tower B5, enters rectifying column B6 rectification, condenser B7 condensation, obtains more than 99% product, baking temperature 20��30oC, rectifying column tower top operation pressure is normal pressure, rectifying tower top operation temperature 65��66oC��
In the embodiment of above 2 kinds, raw material BDO is industrial goods, content 99.1%(GC), moisture 0.2%(KF). Select industrial goods��-Phase nano aluminium oxide, particle diameter 20nm, as catalyst A.
Reaction temperature is preferably 150oC to 350oC, and it is more preferably 170oC to 270oC. Within the scope of said temperature, reaction efficiency is higher. Temperature is lower than 150oC can cause that reaction efficiency is poor, and temperature is higher than 350oC can cause the thermal decomposition of oxolane, thus selectivity can be reduced.
In the methods of the invention, the composition of raw material and product is with gas chromatographic detection (GC):
Select DB-5MS capillary column (30m �� 0.25mm �� 0.25um), Agilent5975 gas chromatograph is analyzed, 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, in stock Product, the detection method of moisture is Karl_Fischer method (KF).
In embodiments of the invention, reaction yield calculates according to below equation:
The amount (mol) �� 100% of the amount (mol) of yield=product oxolane/raw material 1,4-butanediol
Experimental verification:
Method for preparing catalyst 1
The gama-alumina taking 20g is placed in 250mL single port flask, and being subsequently adding concentration is 10wt% magnesium nitrate solution 80g, and room temperature stands 20h. Under vacuum condition, (2.0��2.5kPa) rotary evaporation obtains solid, is squeezed into clover shape, and 110oDry 1h under C, temperature programming is roasting in Muffle furnace: 450oC roasting 1h, 500oC roasting 1h, 550oC roasting 4h. Obtaining catalyst A, magnesium-supported amount is 0.8wt% after testing.
Method for preparing catalyst 2
The gama-alumina taking 20g is placed in 250mL single port flask, is subsequently adding the 8wt% potassium nitrate solution 50g of concentration, and room temperature stands 20h. Under vacuum condition (2.0��2.5kPa), rotary evaporation obtains solid, is squeezed into cylindrical shape, 110oDry 1h under C, temperature programming is roasting in Muffle furnace: 450oC roasting 1h, 500oC roasting 1h, 550oC roasting 4h. Obtaining catalyst B, potassium load capacity is 2.2wt% after testing.
Prepare oxolane experiment 1
3g gama-alumina is added diameter is in 250mL reactor bottle, adds the BDO of 40g, it is heated to reaction to start, has gas to produce, start to drip raw material 1,4-butanediol, constantly steams product, successive reaction 100h simultaneously, collect product, carrying out dewatering after drying, rectification obtains product, calculates after testing: product purity 95.0%(GC), moisture 0.08%(KF), yield is 91%.
Prepare oxolane experiment 2
20g catalyst A is added diameter is in the shell and tube reactor that 8mm length is 400mm, starts nitrogen and purges 3h, starts to use dosing pump with the speed of 5mL/min by BDO liquid input reactor, and heater outlet temperature keeps 160oC, temperature of reactor maintains 170oC, successive reaction 100h, collect product, carries out dewatering after drying, and rectification obtains product, calculates after testing: product purity 99.5%(GC), moisture 0.10%(KF), yield is 95%.
Prepare oxolane experiment 3
20g catalyst B is added diameter is in the shell and tube reactor that 8mm length is 400mm, starts nitrogen and purges 3h, starts to use dosing pump with the speed of 5mL/min by BDO liquid input reactor, and heater outlet temperature keeps 160oC, temperature of reactor maintains 170oC, successive reaction 100h, collect product, carries out dewatering after drying, and rectification obtains product, calculates after testing: product purity 99.3%(GC), moisture 0.08%(KF), yield is 92%.
Prepare oxolane experiment 4
WithPrepare oxolane experiment2, selecting gama-alumina is that catalyst reacts in shell and tube reactor, products obtained therefrom purity 93.8%(GC), moisture 0.11%(KF), yield is 89%.
Table one:
| 1 | 2 | 3 | |
| Catalyst | Magnesium-��-Aluminium oxide | Potassium-��-Aluminium oxide | ��-Aluminium oxide |
| Reaction yield | 95% | 92% | 89% |
As shown in Table 1 it can be seen that substantially high as the obtained reaction yield of reaction of catalyst with modified nano-alumina granule. Therefore, modified nano-alumina granule is used can to realize the high produced in yields of oxolane.
It is evident that from the description above, production method according to embodiments of the present invention, the use of modified catalyst can realize the high produced in yields of oxolane by simple and dangerous low production technology, solves the problem that the reaction yield when producing oxolane is relatively low and is likely to potential danger in process of production simultaneously.
Claims (10)
1. a method for modified nano-alumina catalyst preparing high-purity tetrahydrofuran, at ambient pressure, at modified Nano��-The reaction of BDO dehydration ring closure is carried out, it is characterised in that preparation process is under the effect of aluminium oxide catalyst:
(1) modified modified Nano is added in the reactor��-Aluminium oxide catalyst, adds BDO, 150��350oReact at C temperature, steam after the condensed device of product oxolane condenses then through fraction water device water-dividing, obtain oxolane crude product;
(2) oxolane crude product dries through drying tower, baking temperature 20��30oC; Entering rectifying column rectification, rectifying column tower top operation pressure is normal pressure, rectifying tower top operation temperature 65��66oC;
(3) condense then through condenser, remove a small amount of by-product, obtain the oxolane product that purity is more than 99%.
2. the method for the modified nano-alumina catalyst preparing high-purity tetrahydrofuran described in claim 1, it is characterised in that: described step (1) adds the modified Nano of powder in tank reactor (A1)��-Aluminium oxide catalyst.
3. the method for modified nano-alumina catalyst preparing high-purity tetrahydrofuran as claimed in claim 1, it is characterised in that: in described step (1) in fixing bed tower reactor (B2), add the modified Nano of solid��-Alumina particle, BDO is through preheater (B1) pretreatment, and the activation temperature of pretreatment is 150��200oC��
4. the method for modified nano-alumina catalyst preparing high-purity tetrahydrofuran as claimed in claim 3, it is characterised in that: in described step (1) in fixing bed tower reactor (B2), add the modified Nano of solid��-Alumina particle, BDO is through preheater (B1) pretreatment, and heater outlet temperature keeps 170oC, temperature of reactor maintains 200oC, successive reaction 100 hours.
5. the method for modified nano-alumina catalyst preparing high-purity tetrahydrofuran as claimed in claim 1, it is characterised in that described modified Nano��-The preparation method of aluminium oxide is: general nanometer��-Aluminium oxide joins in the precursor solution of 0.1��15wt% carried metal of concentration, and room temperature stands 24 hours, and under vacuum condition 2.0��2.5kPa, rotary evaporation obtains solid, extrudes balling-up lamellar, cylindric or graininess, 100��130oDrying 1��5 hour under C, temperature programming is roasting in Muffle furnace: 450oC roasting 1��3h, 500oC roasting 1h, 550oCRoasting 4h, is cooled to room temperature, namely obtains modified nano-alumina.
6. the method for modified nano-alumina catalyst preparing high-purity tetrahydrofuran as claimed in claim 5, it is characterised in that described modified Nano��-Aluminium oxide is��-Aluminium oxide granule particle loading potassium, calcium, sodium, zirconium, molybdenum, nickel, tungsten, magnesium, one or more metals in copper, load capacity: 0.1��15wt%.
7. the method for the modified nano-alumina catalyst preparing high-purity tetrahydrofuran as described in claim 3 or 4, it is characterized in that: in fixing bed tower reactor, reactor diameter: catalyst particle size=5��10, reactor length: catalyst particle size=50��100.
8. the method for modified nano-alumina catalyst preparing high-purity tetrahydrofuran as claimed in claim 1, it is characterised in that: filling 4A molecular sieve in drying tower.
9. the method for modified nano-alumina catalyst preparing high-purity tetrahydrofuran as claimed in claim 1, it is characterised in that: rectifying column adopts efficient structured wire corrugated wire gauze packing.
10. the method for the modified nano-alumina catalyst preparing high-purity tetrahydrofuran as described in as arbitrary in claim 1,2,3, it is characterised in that: reaction temperature is 170��270oC��
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| CN106543112A (en) * | 2016-11-02 | 2017-03-29 | 宁夏美邦寰宇化学有限公司 | A kind of infiltrating and vaporizing membrane couples variable-pressure rectification tetrahydrofuran dewatering process |
| CN111659426A (en) * | 2020-06-18 | 2020-09-15 | 大连九信精细化工有限公司 | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 2, 5-dihydrofuran |
| CN116003350A (en) * | 2022-12-16 | 2023-04-25 | 华峰集团上海工程有限公司 | Preparation method of tetrahydrofuran |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106543112A (en) * | 2016-11-02 | 2017-03-29 | 宁夏美邦寰宇化学有限公司 | A kind of infiltrating and vaporizing membrane couples variable-pressure rectification tetrahydrofuran dewatering process |
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| CN111659426A (en) * | 2020-06-18 | 2020-09-15 | 大连九信精细化工有限公司 | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 2, 5-dihydrofuran |
| CN111659426B (en) * | 2020-06-18 | 2023-01-03 | 大连九信精细化工有限公司 | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 2, 5-dihydrofuran |
| CN116003350A (en) * | 2022-12-16 | 2023-04-25 | 华峰集团上海工程有限公司 | Preparation method of tetrahydrofuran |
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