CN1216876C - Preparing method for tetrahydrofuran - Google Patents
Preparing method for tetrahydrofuran Download PDFInfo
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- CN1216876C CN1216876C CN 02153366 CN02153366A CN1216876C CN 1216876 C CN1216876 C CN 1216876C CN 02153366 CN02153366 CN 02153366 CN 02153366 A CN02153366 A CN 02153366A CN 1216876 C CN1216876 C CN 1216876C
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Abstract
The present invention relates to a method for preparing tetrahydrofuran. The method comprises the following steps: raw material which contains 1, 4-butanediol contacts eta-Al2O3 catalysts; the raw material reacts with the catalysts under the conditions that the reaction temperature is from 170 to 350 DEG C, the pressure is from 0.1 to 1.0MPa and the time space speed of raw material liquid is from 1 to 150h<-1>, and products are collected, wherein the specific surface area of eta-Al2O3 is from 100 to 260m<2>/g, and the pore volume is from 0.1 to 1.0 ml/g. The method for preparing tetrahydrofuran, which is provided by the present invention, has the characteristics that the price of eta-Al2O3 used for dehydration and cyclisation is low, eta-Al2O3 is easily obtained, the preparation is simple, eta-Al2O3 does not need to be processed before being used, the activity is high, and the processing capacity is large; the mixed material which contains the 1, 4-butanediol does not need to be separated, the dehydration and cyclisation reaction can be directly carried out, a separation step is cancelled, the technical process is simplified, and the investment and the operating cost are reduced.
Description
Technical field
The present invention relates to the preparation method of tetrahydrofuran (THF).
Technical background
Tetrahydrofuran (THF) (Tetrahydrofuran) is called for short THF, be important basic Organic Chemicals, it is the low boiling point solvent of excellent property, and main application is to produce polytetramethylene support glycol ether (PTMEG) and make polyurethane elastomeric fiber, elastomerics and polyurethane artificial leather etc., also can be used for printing ink, paint remover, extraction agent, in the artificial surfaces treatment agent, also can be used as polyreaction, the solvent in the esterification also is widely used in medicine industry and accurate tape industry.
At present, production method has three kinds, furfural method, maleic anhydride hydrogenation method and 1,4-butyleneglycol cyclodehydration method.Wherein the furfural method is because complex process, and the raw material consumption height seriously pollutedly is eliminated gradually.The maleic anhydride hydrogenation method, with the cis-butenedioic anhydride is raw material, at first that it is soluble in water, make 35% the aqueous solution,, must adopt expensive anticorrosion material because the cis-butenedioic anhydride aqueous solution has very strong corrodibility, in addition, need with precious metals pd-Re/C catalyzer, and carry out hydrogenation under the high pressure of 17-35Mpa, these all make the fixed investment of this technology and process cost significantly rise.
1,4-butyleneglycol cyclodehydration method is the more method of using at present, opens clear 51-76263 as the spy and discloses a kind of with SiO
2-Al
2O
3As catalyzer, prepare the method for tetrahydrofuran (THF), it adopts fixed bed to carry out gas-solid phase reaction, at 250 ℃, SiO
2Content is 87% SiO
2-Al
2O
3Under the catalyst action, the tetrahydrofuran (THF) yield is 97%, 1, and the processing power of 4-butyleneglycol is a 1g/g catalyzer hour.SU 1426973 discloses a kind of preparation method of tetrahydrofuran (THF), is that the 4-butyleneglycol is a raw material, with γ-Al with pure 1
2O
3Or η-Al
2O
3Be catalyzer, wherein η-Al
2O
3Specific surface area be 350-500m
2/ g, the catalyzer maximum processing capability has only 10.5h
-1
In sum, though the existing method for preparing tetrahydrofuran (THF) has multiple, but exist seriously polluted respectively, raw material consumption height or reaction pressure height, catalyzer costliness, problems such as device requirement for anticorrosion height, adopt 1,4-butyleneglycol cyclodehydration technology also exists liquid hourly space velocity low, the defective that the catalyst treatment ability is low.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of preparation method of tetrahydrofuran (THF) is provided.
The preparation method of tetrahydrofuran (THF) provided by the invention comprises:
To contain 1, the raw material of 4-butyleneglycol and η-Al
2O
3The catalyzer contact is 170-350 ℃ in temperature of reaction, and preferred 220-320 ℃, pressure is 0.1-1.0Mpa, preferred 0.1-0.5Mpa, and the stock liquid hourly space velocity is 1-150h
-1, preferred 1-110h
-1Condition under react, collect product.
Said η-Al
2O
3Characteristic is as follows: specific surface 100-260m
2/ g, preferred 170-215m
2/ g, pore volume 0.1-1.0ml/g, preferred 0.3-0.7ml/g.η-Al
2O
3Catalyzer is by visiing diaspore or visit diaspore and the mixture roasting of promise diaspore obtains, and maturing temperature 300-900 ℃, preferred 400-700 ℃, roasting time 0.5-20 hour, preferred 1-15 hour.
Saidly contain 1, can also contain other organism such as tetrahydrofuran (THF), low-carbon alcohol, gamma-butyrolactone in the raw material of 4-butyleneglycol.Other organic existence does not influence catalyst activity, only influences the yield of purpose product, but considers that from the Technological Economy angle other organic content preferably is no more than 70%.
Because the inventive method can be handled and contain 1, the mixture of 4-butyleneglycol, therefore, in industrial production, what the di-carboxylic acid ester through hydrogenation can be obtained contains 1, the mixture of 4-butyleneglycol and gamma-butyrolactone directly as the raw material of the inventive method, so just can be realized purpose of producing tetrahydrofuran (THF) and gamma-butyrolactone in parallel in a cover technology.Specifically, dicarboxylic esters and hydrogen are fed in the reactor together, behind first section hydrogenation catalyst, reacting coarse product need not separate, and continues by second section η-Al
2O
3The cyclodehydration catalyzer, get final product tetrahydrofuran (THF) and gamma-butyrolactone.
Disclosing multiple in the prior art is feedstock production 1 with the dicarboxylic esters, 4-butyleneglycol method, and preferred following method:
Toxilic acid and/or succinate and hydrogen are fed in the reactor, with general formula be CuMn
aAl
bO
cMetal composite oxide catalyst contact, wherein, a=0.04-4, preferred 0.1-3.2; B=0.04-4, preferred 0.08-3.5, c is the oxygen atomicity that satisfies other element valence requirement.
The processing condition of hydrogenation are: adopt the fixed bed mode, temperature of reaction is 170-250 ℃, and preferred 180-220 ℃, pressure is 2.0-7.0Mpa, preferred 3.0-6.0Mpa, and the air speed of ester is 0.1-15h
-1, preferred 0.7-12h
-1, more preferably 1-9h
-1, hydrogen/ester mol ratio is 5-500: 1, and preferred 100-300.
Said hydrogenation catalyst can be prepared as follows: the soluble salt of Cu, Mn, Al is dissolved in the deionized water, under 10-80 ℃ with alkali precipitation to PH=4-11, aging 0-5 hour, filter then, washing, collecting precipitation, in 60-200 ℃ of dry 2-30 hour, in 300-900 ℃ of roasting 2-30 hour, promptly get said catalyzer again.Wherein soluble salt can be the solution that contains Cu, Mn, three kinds of metal-salts of Al simultaneously, also can be only to contain the wherein solution of one or both metal-salts, if the latter can use alkali precipitation respectively with several solution that contain different metal salt earlier, again reacted solution is mixed the back and wear out.
The preferred nitrate separately of the soluble salt of said Cu, Mn, Al.
Said alkali can be volatile salt, bicarbonate of ammonia, ammoniacal liquor, yellow soda ash, sodium hydroxide and potassium hydroxide etc., preferred volatile salt, bicarbonate of ammonia, ammoniacal liquor.The concentration of alkali lye is 5-4096, preferred 10-3596.
Said hydrogenation catalyst need give reduction before using, and reductive agent can adopt reducing gas such as hydrogen, carbon monoxide, and reduction is carried out under 0.1-2.0MPa, 150-300 ℃ condition, and the reducing gas flow is 50-500ml/min for every milliliter of catalyzer.
Tetrahydrofuran (THF) preparation method provided by the invention has following characteristics: the used η-Al of (1) cyclodehydration
2O
3Cheap and easy to get, preparation is simple, need not carry out any processing before use, and active high, and processing power is big.(2) contain 1, the mixture of 4-butyleneglycol need not separate, and can directly carry out the cyclodehydration reaction, has saved separating step, and technical process is simplified, and investment and process cost reduce.
Embodiment
Example 1-3 is the preparation of hydrogenation catalyst
Example 1
With 52.2g Cu (NO
3)
2.3H
2O (Beijing Chemical Plant's product, chemical pure), 23.2g 50% Mn (NO
3)
2. the aqueous solution (Beijing Chemical Plant's product, chemical pure), 8.1g Al (NO
3)
3.9H
2O (Beijing Chemical Plant's product, chemical pure) is dissolved in the 600ml deionized water, stirs down at 50 ± 1 ℃, drip 12wt% ammoniacal liquor (Beijing Chemical Plant's product, chemical pure), be 5.5 ± 0.5 until the pH of solution, aging 1 hour, filter then, washing once, collecting precipitation, 200 ℃ of dryings 2 hours, accompany for 500 ℃ and burnt 2 hours, promptly get catalysis A:CuMn
0.15Al
0.1O
1.3
Example 2
With 35.5g Cu (NO
3)
2.3H
2O (Beijing Chemical Plant's product, chemical pure), 105g 50% Mn (NO
3)
2. the aqueous solution (Beijing Chemical Plant's product, chemical pure), 118g Al (NO
3)
3.9H
2O (Beijing Chemical Plant's product, chemical pure) is dissolved in the 1000ml deionized water, at room temperature drip 30wt% carbonic acid ammonia, until solution PH is 9.0 ± 0.5, aging 1 hour, filter then, wash once, collecting precipitation, 200 ℃ of dryings 2 hours, accompany for 750 ± 10 ℃ and burnt 18 hours, promptly get catalyst B: CuMn
2.7Al
2.9O
8.1
Example 3
With 52.2g Cu (NO
3)
2.3H
2O, 70g 50% Mn (NO)
2. the aqueous solution, 32.5g Al (NO
3)
3.9H
2O is dissolved in the 500ml deionized water, makes solution A.(25 heavy %) makes solution B with yellow soda ash.The 400ml deionized water of in the 2000ml beaker, packing into, under agitation add in the beaker simultaneously two kinds of solution of A.B, control A.B drips speed, makes PH remain at 7.6 ± 0.5, wears out 1 hour after the titration, filter then, through 5 washings, collecting precipitation was 120 ℃ of dryings 12 hours, 800 ℃ of roastings 7 hours promptly get catalyzer C:CuMn
0.87Al
0.4O
2.5
Example 4-6 is η-Al
2O
3Preparation of catalysts
Example 4
50g is contained promise diaspore and the mixing aqueous alumina (wherein visiing diaspore 70%) of visiing diaspore, place muffle furnace,, can obtain η-Al at 400 ℃ of roasting 4hr
2O
3Catalyzer D, specific surface 215m
2/ g, pore volume 0.57ml/g.
Example 5
50g is contained promise diaspore and the mixing aqueous alumina (wherein visiing diaspore 30%) of visiing diaspore, place muffle furnace,, can obtain η-Al at 500 ℃ of roasting 10hr
2O
3Catalyzer E, specific surface 200m
2/ g pore volume 0.40ml/g.
Example 6
50g is visitd diaspore place muffle furnace,, can obtain η-Al at 700 ℃ of roasting 2hr
2O
3Catalyzer F, specific surface 170m
2/ g, pore volume 0.31ml/g.
Example 7～9 is the catalyzed reaction example
Hydrogenation catalyst gives processing: under 200 ℃, 2.0Mpa condition with the flow velocity of 100ml/ming catalyzer, logical H
2Reductase 12 0hr.
Example 7
With the dimethyl maleate is raw material, and catalyst A is first section catalyzer, and hydrogenation conditions is 189 ± 1 ℃, 5.8 ± 0.2Mpa, H
2269: 1 (mol) stock liquids of/ester hourly space velocity 1.8h
-1React under the condition, catalyzer D is second section catalyzer, 300 ± 2 ℃ of reaction conditionss, 0.1Mpa, liquid hourly space velocity 90h
-1, products therefrom detects through FID with the gas chromatograph of PEG20000 packed column, the results are shown in Table 1.
Table 1
| Hydrogenation products | Raw material | Transformation efficiency/mol% | Selectivity/mol% | |||
| Tetrahydrofuran (THF) | Butanols | Gamma-butyrolactone | 1, the 4-butyleneglycol | |||
| One section two sections total | One section product dimethyl maleate of dimethyl maleate | 100 90 100 | 1.3 99.8 77.6 | 0.72 0.72 | 13.0 13.0 | 85 - 8.5 |
Example 8
With the dimethyl maleate is raw material, and catalyst B is first section catalyzer, and hydrogenation conditions is 189 ± 1 ℃, 5.8 ± 0.2Mpa, H
2140: 1 (mol) stock liquids of/ester hourly space velocity 3.7h
-1React under the condition, catalyzer E is second section catalyzer, 300 ± 2 ℃ of reaction conditionss, 0.3Mpa, liquid hourly space velocity 45h
-1, the results are shown in Table 2.
Table 2
| Hydrogenation products | Raw material | Transformation efficiency/mol% | Selectivity/mol% | |||
| Tetrahydrofuran (THF) | Butanols | Gamma-butyrolactone | 1, the 4-butyleneglycol | |||
| One section two sections total | One section product dimethyl maleate of dimethyl maleate | 100 98.6 100 | 1.8 99.9 76.7 | 1.1 1.1 | 21.0 21.0 | 76 - 1.1 |
Example 9
With the dimethyl maleate is raw material, and catalyzer C is first section catalyzer, and hydrogenation conditions is 189 ± 2 ℃, 5.8 ± 0.2Mpa, H
293: 1 (mol) stock liquids of/ester hourly space velocity 9.1h
-1React under the condition, catalyzer F is second section catalyzer, 244 ℃ of reaction conditionss, 0.3Mpa, liquid hourly space velocity 5.4h
-1, the results are shown in Table 3.
Table 3
| Hydrogenation products | Raw material | Transformation efficiency/mol% | Selectivity/mol% | |||
| Tetrahydrofuran (THF) | Butanols | Gamma-butyrolactone | 1, the 4-butyleneglycol | |||
| One section two sections total | One section product dimethyl maleate of dimethyl maleate | 100 99.3 100 | 7.2 99.9 62.6 | 4.4 4.4 | 32.5 32.5 | 55.8 - 0.4 |
Claims (8)
1. the preparation method of a tetrahydrofuran (THF) comprises: will contain 1, the raw material of 4-butyleneglycol and η-Al
2O
3The catalyzer contact is 170-350 ℃ in temperature of reaction, and pressure is 0.1-1.0Mpa, and the stock liquid hourly space velocity is 1-150h
-1Condition under react, collect product, wherein η-Al
2O
3Specific surface is 100-260m
2/ g, pore volume are 0.1-1.0ml/g, said η-Al
2O
3Obtain by the mixture roasting of visiing diaspore and promise diaspore.
2. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 220-320 ℃, pressure is 0.1-0.5Mpa, and the stock liquid hourly space velocity is 1-110h
-1
3. in accordance with the method for claim 1, it is characterized in that said η-Al
2O
3Specific surface is 170-215m
2/ g, pore volume are 0.3-0.7ml/g.
4. in accordance with the method for claim 1, it is characterized in that said η-Al
2O
3Obtain by the mixture roasting of visiing diaspore and promise diaspore, maturing temperature 300-900 ℃, roasting time 0.5-20 hour.
5. in accordance with the method for claim 4, it is characterized in that, maturing temperature 400-700 ℃, roasting time 1-15 hour.
6. in accordance with the method for claim 1, it is characterized in that saidly contain 1, the raw material of 4-butyleneglycol is prepared by following method: toxilic acid and/or succinate and hydrogen are fed in the reactor, with general formula be CuMn
aAl
bO
cMetal composite oxide catalyst contact, be 170-250 ℃ in temperature, pressure is 2.0-7.0Mpa, the air speed of ester is 0.1-15h
-1, hydrogen/ester mol ratio is 5-500: reaction and collection product under 1 the condition, wherein, a=0.04-4, b=0.04-4, c are the oxygen atomicities that satisfies other element valence requirement.
7. in accordance with the method for claim 6, it is characterized in that a=0.1-3.2, b=0.08-3.5.
8. in accordance with the method for claim 6, it is characterized in that temperature of reaction is 180-220 ℃, pressure is 3.0-6.0Mpa, and the air speed of ester is 0.7-12h
-1, hydrogen/ester mol ratio is 5-500: 1.
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|---|---|---|---|
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|---|---|---|---|
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