CN103044367B - Production method of gamma-butyrolactone - Google Patents
Production method of gamma-butyrolactone Download PDFInfo
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- CN103044367B CN103044367B CN201110313277.6A CN201110313277A CN103044367B CN 103044367 B CN103044367 B CN 103044367B CN 201110313277 A CN201110313277 A CN 201110313277A CN 103044367 B CN103044367 B CN 103044367B
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Abstract
The invention relates to a method for producing gamma-butyrolactone through dehydrogenation of 1,4-butanediol. A catalyst is composed of CuO-ZnO-Al2O3 and assistant K and/or Li impregnated on the surface of CuO-ZnO-Al2O3; the catalyst comprises 37-52% of CuO, 40-55% of ZnO, 7-9.5% of Al2O3 and a proper mixture ratio of assistant K and/or Li; and the catalyst is free of Cr. When the catalyst is used under the conditions that the reaction temperature is 230-250 DEG C, the reaction pressure is 0-0.4 MPa, the feeding airspeed is 1.0-2.5 h<-1> and the hydrogen/alcohol mol ratio is 3-10, the conversion rate of 1,4-butanediol can be up to 98%, and the selectivity of gamma-butyrolactone can be up to 99% or above.
Description
Technical field
The invention relates to BDO in the presence of a catalyst gas-phase dehydrogenation produce the method for gamma-butyrolactone.
Background technology
Gamma-butyrolactone (γ-Butyrolactone is called for short γ-BL or GBL), call as GBL, molecular formula is C
4h
6o
2.Himself structure is a kind of compound containing 5-membered heterocycles, and gamma-butyrolactone is a kind of colourless liquid, has the smell of similar acetone, has high boiling point and high dissolving power, can water-soluble, methyl alcohol, ethanol, acetone, ether and benzene preferably.Its reactivity worth is good, and specific conductivity is high, good stability, use safety.As a kind of important organic solvent, gamma-butyrolactone is widely used in many aspects such as petroleum industry, medicine, synthon, synthetic resins, agricultural chemicals.As a kind of important fine chemistry industry and Organic Chemicals, be mainly used in the products such as synthesis of pyrrolidine ketone, N-Methyl pyrrolidone, vinyl pyrrolidone, and many new purposes are constantly under development.
After first M.B.Chanlatoft in 1884 uses 4 hydroxybutyric acid intramolecular esterification synthetic gamma butyrolactone, people have carried out a large amount of deep research to the synthesis of gamma-butyrolactone and production technology, existing different Technology
route carries out industrial production, according to the raw material classification of synthesis, mainly contains following three kinds of methods: furfural method, cis-butenedioic anhydride (MA) hydrogenation method and BDO (BDO) dehydriding.Furfural method process is complicated, and cost is higher, loses the market competitiveness, and this method is eliminated at present, and maleic anhydride hydrogenation method raw material is easy to get, and cost is low, but in crude product, acidity is relatively high, and this brings certain impact to the separation of product and the quality of end product.1, by product mainly tetrahydrofuran (THF) (THF) and a small amount of butanols (BOL) of 4-butanediol dehydrogenation method, component is simple, and product is easily separated, the gamma-butyrolactone quality better of synthesis, can meet as pharmaceutical raw material and battery electrolyte the high request of gamma-butyrolactone quality.
1,4-butanediol dehydrogenation used catalyst is based on Cu-Cr series catalysts, as United States Patent (USP) 5210229 adopts Cu-Cr-Mn and/or Ba catalyzer, add Alkali-Metal Na or K modification, although reduce the acidity of catalyzer, decrease dehydration reaction, but reduce the activity of catalyzer, need to improve temperature of reaction to compensate (being increased to 270 DEG C from 230 DEG C), as at 230 DEG C, H
2/ alcohol (mole)=4:1, pressure 4kg/cm
2(table), weight space velocity 3.0h
-1time, BDO transformation efficiency 91.39%, gamma-butyrolactone selectivity 98.98%, tetrahydrofuran (THF) selectivity 0.14%, improve temperature to 270 DEG C, above three are then respectively 99.49%, 97.93% and 0.17%.61-246173(1986 as clear in Japanese Patent), adopt Cu-Cr-Zn catalyzer, it forms Cu:Cr:Zn=35:68:38, when temperature of reaction 228 DEG C, in product, gamma-butyrolactone content is 98.2wt%, Japanese Patent JP03,232,874 (1991), adopt Cu-Cr-Ba catalyzer, wherein Cu:Cr:Ba=47:42:6,230 DEG C time, BDO transformation efficiency 96.1mol%, gamma-butyrolactone selectivity 95.1 mol%.What adopt Cu-Cr series catalysts also has: EP523774A, CN1173492, CN1194268, CN1169428, CN1220186A.Although can improve the yield of gamma-butyrolactone containing Cr catalyzer, the Cr element in catalyzer can cause environmental pollution, and to human health, therefore people are developing not containing the catalyzer of Cr always, as the Cu/SiO that US6093677 adopts pickling process to prepare
2-CaO catalyzer, gas-phase dehydrogenation, at temperature of reaction 190-230 DEG C, pressure 1-2bar, air speed 0.5-7.5kg/kgCu.h, BDO transformation efficiency is greater than 99%, and gamma-butyrolactone selectivity is greater than 97%.Also just like catalyzer such as Cu-Zn, Pt, Pd, wherein based on Cu-Zn catalyzer, difference is, adds different auxiliary agents to improve the reactivity worth of catalyzer in concrete preparation process.As CN1111168, used catalyst is made up of Cu-Zn-Al oxide matrix and spraying Pd or Pt thereon, temperature of reaction 190-290 DEG C, reaction pressure normal pressure, use this catalyzer under hydrogen alcohol mol ratio 1-6 condition, 1,4-butyleneglycol transformation efficiency can reach 100%, and gamma-butyrolactone selectivity can reach 97%.CN1304795, adopt Cu-Zn-Al catalyzer, auxiliary agent is at least one in BaO, Pd two kinds, and at temperature of reaction 200-260 DEG C, reaction pressure is less than 0.05MPa, liquid hourly space velocity 0.1-1.2h
-1, BDO transformation efficiency can reach 100%, and gamma-butyrolactone selectivity is greater than 96%.CN1562473 adopts CuO-ZnO-Ce
2o
3catalyzer, Ce
2o
3content is 2-3%, and at temperature of reaction 210-260 DEG C, reaction pressure is less than 0.05MPa, liquid hourly space velocity 0.1-0.7h
-1, BDO transformation efficiency is greater than 98%, and gamma-butyrolactone selectivity is greater than 95%.
CN99113276.9 discloses a kind of preparation method of copper containing catalyst, cupric oxide 10% ~ 90% in the catalyzer obtained, the oxide compound of co catalysis composition is 0% ~ 50%, aluminum oxide is 5% ~ 40%, comprise the alkalimetal oxide of 0.1% ~ 4.0% simultaneously, this catalyzer may be used for hydrogenation or the dehydrogenation reaction of organic reaction, wide range described in this patent, when the catalyzer that embodiment obtains is produced for gamma-butyrolactone, result of use is unsatisfactory, be mainly manifested in 1, there is more dehydration reaction and generate tetrahydrofuran (THF) in 4-butyleneglycol, the selectivity of gamma-butyrolactone is deteriorated.
Summary of the invention
Not enough for prior art, the invention provides a kind of production method of gamma-butyrolactone, adopt the catalyzer of suitable composition, at lower temperature of reaction, higher liquid hourly space velocity, moderate hydrogen/alcohol ratio and close under condition of normal pressure, the transformation efficiency of BDO dehydrogenation can reach more than 98%, the selectivity of gamma-butyrolactone can reach more than 99%, resultant of reaction component is simple, and product is easily separated, the gamma-butyrolactone quality better produced.
The production method of gamma-butyrolactone of the present invention comprises following content: take BDO as raw material, carries out dehydrogenation reaction and produces gamma-butyrolactone, and catalyzer uses the CuO-ZnO-Al containing K element and/or Li element auxiliary agent
2o
3catalyzer, catalyzer composition comprises by weight: CuO 37% ~ 52%, ZnO 40% ~ 55%, Al
2o
37% ~ 9.5%; Be preferably CuO 42% ~ 50%, ZnO 42% ~ 50%, Al
2o
37% ~ 9.5%; The mol ratio of auxiliary agent K element and/or Li element and Al element is 0.10 ~ 0.25, is preferably 0.15 ~ 0.22.Reaction pressure (gauge pressure) 0 ~ 0.4MPa; Temperature of reaction 220 ~ 270 DEG C, preferably 230 ~ 250 DEG C; Liquid feed volume air speed 0.5 ~ 3.5h
-1, preferably 1.0 ~ 2.5h
-1; Charging H
2/ BDO mol ratio 3:1 ~ 10:1.
Not containing Cr in the catalyzer used in the inventive method.
In the prior art, BDO dehydrogenation is produced to the reaction of gamma-butyrolactone, although Cu-Cr series catalysts reactivity worth is better, can work the mischief to environmental and human health impacts, Cu/SiO prepared by pickling process
2catalyzer price costly, and mainly adds precious metal to improve activity in Cu-Zn composite oxide catalysts, the liquid hourly space velocity of simultaneous reactions is lower.Although Cu-Zn-Al composite oxide catalysts has application in other reaction, but existing Cu-Zn-Al composite oxide catalysts, or the Cu-Zn-Al composite oxide catalysts containing auxiliary agent, for 1, when 4-butanediol dehydrogenation produces gamma-butyrolactone reaction, its reactivity worth all needs further raising.The present invention is found by research, adopts the Cu-Zn-Al composite oxide catalysts of suitable composition, and auxiliary agent K and/or Li of the Optimum Contents of load simultaneously, not only can improve the activity of catalyzer, can also improve selectivity of catalyst.Catalyzer of the present invention containing the chromium component of BDO dehydrogenation reaction custom catalysts, does not avoid problem of environmental pollution.
Specific embodiments
The catalyzer that the inventive method uses is with CuO-ZnO-Al
2o
3precursor catalyst is precursor, and further dip loading K and/or Li element obtain final catalyzer.CuO-ZnO-Al
2o
3precursor catalyst, adopt conventional coprecipitation method to prepare, nitrate by copper, zinc makes the aqueous solution, coprecipitation reaction is completed with basic solution sodium carbonate or sodium bicarbonate, the subcarbonate generated filters washing after aging, add aluminium hydroxide, then drying, roll, granulation, calcining, these processes shaping, make the cylindrical precursor catalyst of Φ 5 × 4 ~ 5mm.Above-mentioned CuO-ZnO-Al
2o
3detailed process prepared by precursor catalyst and condition are well known to those skilled in the art.
Next step will prepare finished catalyst, the nitrate of K and/or Li is made the aqueous solution, usually the aqueous solution of different concns is made into as required, the aqueous solution of 1.0-1.2mol/L is made in the present invention, with the precursor catalyst more than this solution impregnation made, and at 80-100 DEG C reflux 2-6 hour, by dry for the catalyzer after dipping, and namely roasting obtains finished catalyst at 380-590 DEG C.
Catalyzer obtained is above used for 1,4-butanediol Dehydrogenation For Producing Butyrolactone, cylindrical catalyst particle by certain volume is contained in stainless steel tubular reactor, reaction needs before carrying out first to carry out conventional reduction treatment to catalyzer, make the copper of oxidation state become reduction-state, after reduction, with pump, alcohol is delivered into reactor.Because react for gas-phase dehydrogenation reaction, in order to improve material gasification effect, prevent butyleneglycol coking, also need in reaction process to pass into hydrogen or nitrogen, because of the good heat conductivity of hydrogen, and the metallic reducing state of catalyst surface can be maintained very well, therefore select hydrogen in the present invention.
Reaction product is after the gas-liquid separator cooling of reactor outlet, and gas can loop back reactor, also can emptying, forms after liquid product collection with gas chromatographic analysis.
Embodiment 1
By the method described in embodiment, the catalyst A that the inventive method being prepared into following composition uses, B, C, D, E.The reactivity worth of catalyzer is shown in embodiment 2-6, and transformation efficiency wherein and selectivity calculate with molar weight.
Table 1 catalyzer composition (chemical analysis data)
Composition wt% | CuO | ZnO | Al 2O 3 | K/Al mol ratio | Li/Al mol ratio |
A | 45.5 | 46.1 | 7.4 | 0.17 | / |
B | 45.6 | 45.0 | 8.2 | 0.20 | / |
C | 46.5 | 42.9 | 9.1 | 0.11 | 0.08 |
D | 44.8 | 46.3 | 8.5 | / | 0.17 |
E | 45.7 | 45.5 | 8.4 | / | 0.21 |
Embodiment 2
By B catalyzer 20ml 20ml porcelain ring dilution, be encased in fixed-bed reactor, reactor height about 1.7m, internal diameter 25mm, built-in Thermal couple casing pipe, reactor has 6 sections of heating by electric cookers, corresponding 6 thermocouple temperature controls, catalyzer is contained in the 4th section, its complementary space of reactor all uses porcelain ring filling, and adopt upper feeding mode, 1 to 3 section, top is as raw material 1, the gasification section of 4-butyleneglycol is by raw material preheating and gasify, and then enters catalyst layer.
Reaction procatalyst hydrogen reducing, amounts of hydrogen is 10L/hr, and reduction temperature is 200 DEG C, and the recovery time is 8-10 hour, and after reduction terminates, by cooking noodle, part reacts, temperature 240 DEG C; Volume space velocity 1.5h during feeding liquid
-1; H
2/ alcohol mol ratio 5:1, BDO transformation efficiency 98.5%; Gamma-butyrolactone selectivity 99.4%.
Embodiment 3
Reaction unit is identical, catalyst levels and reductive condition identical with embodiment 2, select C catalyst in table 1, by cooking noodle, part reacts, temperature 250 DEG C; Feeding liquid hourly space velocity 1.8h
-1; H
2/ alcohol mol ratio 3:1; BDO transformation efficiency 98.9%, gamma-butyrolactone, gamma-butyrolactone selectivity 99.5%.
Embodiment 4
Reaction unit is identical, catalyst levels and reductive condition identical with embodiment 2, select E catalyzer in table 1, by cooking noodle, part reacts, temperature 235 DEG C; Feeding liquid hourly space velocity 2.0h
-1; H
2/ alcohol mol ratio 7:1; BDO transformation efficiency 97.3%, gamma-butyrolactone selectivity 99.6%.
Embodiment 5
Select A catalyzer in table 1, other condition is with embodiment 2, and reaction result is BDO transformation efficiency 98.0%, gamma-butyrolactone selectivity 99.6%.
Embodiment 6
Select D catalyzer in table 1, other condition is with embodiment 2, and reaction result is BDO transformation efficiency 97.8%, gamma-butyrolactone selectivity 99.1%.
Comparative example 1
By CuO-ZnO-Al prepared by CN99113276.9
2o
3-base metal catalysts A(consists of CuO45.4%; ZnO35.1%; Al
2o
318.3%; K
2o 1.2%) and E(consist of CuO45.3%; ZnO35.0%; Al
2o
318.2%; Cs
2o1.5%), according to the reaction conditions of embodiment 2, reaction result when using catalyst A is BDO transformation efficiency 97.2%, gamma-butyrolactone selectivity 94.2%., reaction result when using catalyzer E is BDO transformation efficiency 97.6%, gamma-butyrolactone selectivity 95.5%.Can find out, gamma-butyrolactone selectivity ratios the inventive method is low about 5 percentage points.
Claims (10)
1. a production method for gamma-butyrolactone take BDO as raw material, carries out dehydrogenation reaction and produces gamma-butyrolactone, it is characterized in that: catalyzer uses the CuO-ZnO-Al containing K element and/or Li element auxiliary agent
2o
3catalyzer, catalyzer composition is by weight: CuO 37% ~ 52%, ZnO 40% ~ 55%, Al
2o
37% ~ 9.5%, the mol ratio of auxiliary agent K element and/or Li element and Al element is 0.10 ~ 0.25.
2. in accordance with the method for claim 1, it is characterized in that: the reaction pressure of dehydrogenation reaction is 0 ~ 0.4MPa, temperature of reaction 220 ~ 270 DEG C, liquid feed volume air speed 0.5 ~ 3.5h
-1, charging H
2/ BDO mol ratio 3:1 ~ 10:1.
3. according to the method described in claim 1 or 2, it is characterized in that: temperature of reaction is 230 ~ 250 DEG C.
4. according to the method described in claim 1 or 2, it is characterized in that: liquid feed volume air speed is 1.0 ~ 2.5h
-1.
5. in accordance with the method for claim 1, it is characterized in that: catalyzer is with CuO-ZnO-Al
2o
3precursor catalyst is precursor, and further dip loading K and/or Li element obtain final catalyzer.
6. in accordance with the method for claim 5, it is characterized in that: CuO-ZnO-Al
2o
3precursor catalyst adopts conventional coprecipitation method preparation, the aqueous solution is made by the nitrate of copper, the nitrate of zinc, coprecipitation reaction is completed with basic solution sodium carbonate or sodium bicarbonate, the subcarbonate generated filters washing after aging, add aluminium hydroxide, again drying, roll, granulation, calcining, these processes shaping, make precursor catalyst.
7. in accordance with the method for claim 5, it is characterized in that: CuO-ZnO-Al
2o
3the method that precursor catalyst prepares final catalyzer is that the nitrate of K and/or Li is made the aqueous solution, and the concentration of solution is 1.0-1.2mol/L, with this solution impregnation CuO-ZnO-Al
2o
3precursor catalyst, and at 80-100 DEG C reflux 2-6 hour, by dry for the catalyzer after dipping, and namely roasting obtains finished catalyst at 380-590 DEG C.
8. in accordance with the method for claim 1, it is characterized in that: the mol ratio of auxiliary agent K element and/or Li element and Al element is 0.15 ~ 0.22.
9. according to the method described in claim 1 or 8, it is characterized in that: catalyzer composition comprises by weight for CuO 42% ~ 50%, ZnO 42% ~ 50%, Al
2o
37% ~ 9.5%.
10. in accordance with the method for claim 1, it is characterized in that: catalyzer is not containing Cr.
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CN104549399B (en) * | 2013-10-23 | 2017-02-15 | 中国石油化工股份有限公司 | Shell catalyst for 1, 4-butanediol vapor-phase dehydrogenation and application of shell catalyst |
CN103877981B (en) * | 2014-01-07 | 2017-02-08 | 迈奇化学股份有限公司 | Catalyst for preparing gamma-butyrolactone by gaseous phase dehydrogenation of 1, 4-butanediol under normal pressure and preparation method thereof |
JP7195116B2 (en) | 2017-11-14 | 2022-12-23 | 中国石油化工股▲ふん▼有限公司 | Copper-based catalysts, methods of making the same, and uses thereof |
CN112742432B (en) * | 2019-10-30 | 2022-09-20 | 中国石油化工股份有限公司 | Method for preparing gamma-butyrolactone by maleic anhydride hydrogenation |
CN112756004B (en) * | 2019-11-04 | 2022-09-20 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone by maleic anhydride hydrogenation and preparation method and application thereof |
CN115779957B (en) * | 2022-12-10 | 2024-03-19 | 南通格瑞凯泰工程技术有限公司 | Catalyst for preparing gamma-butyrolactone by low-pressure dehydrogenation of 1, 4-butanediol and application thereof |
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