CN100366338C - Catalyst for preparing gamma-butyrolactone by normal pressure gas phase hydrogenation of maleic-anhydride and preparation process thereof - Google Patents
Catalyst for preparing gamma-butyrolactone by normal pressure gas phase hydrogenation of maleic-anhydride and preparation process thereof Download PDFInfo
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- CN100366338C CN100366338C CNB2004100990737A CN200410099073A CN100366338C CN 100366338 C CN100366338 C CN 100366338C CN B2004100990737 A CNB2004100990737 A CN B2004100990737A CN 200410099073 A CN200410099073 A CN 200410099073A CN 100366338 C CN100366338 C CN 100366338C
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Abstract
The present invention discloses a catalyst for preparing gamma-butyrolactone by the gas-phase hydrogenation of maleic anhydride at normal pressure, and a preparation method thereof. The catalyst of the present invention is composed of CuO, TiO2, Al2O3 and an auxiliary agent and can be prepared with a coprecipitation method or a microemulsion method. The catalyst of the present invention contains no toxic component Cr and belongs to an environmental protection type catalyst. The catalyst has high conversion rate of maleic anhydride and high selectivity of gamma-butyrolactone under the high liquid hourly space velocity of the maleic anhydride, and the conversion rate of maleic anhydride and the selectivity of the gamma-butyrolactone can respectively reach 100 %. Even when the reaction occurs, and the catalyst activity is reduced, the selectivity of gamma-butyrolactone can also be kept for 100%; thereby, the product separation is convenient. The catalyst of the present invention has the advantages of favorable catalytic performance, high one-way yield of gamma-butyrolactone, and simple operation process and is a catalyst which has a high price ration and is used for preparing gamma-butyrolactone by the gas-phase hydrogenation of maleic anhydride at normal pressure.
Description
Technical field
The present invention relates to a kind of cis-anhydride normal pressure hydrogenation preparing gama-butalactone Catalysts and its preparation method, specifically, be at least a cis-anhydride normal pressure hydrogenation preparing gama-butalactone catalyst that mixes in a kind of Cu of containing, Ti, Al and Mg, Ba, Zn, Sn, La, six kinds of elements of Ni.
Background technology
Gamma-butyrolacton (γ-Butyrolactone, be called for short GBL) is a kind of colourless oily liquid, has that good stability, solvability are strong, a good conductivity, characteristics such as safe in utilization, is a kind of good high boiling organic solvent.The chemical reaction of a series of open loops or not open loop can take place in GBL, be important Organic Chemicals and fine-chemical intermediate, can be used for the derived product of synthetic many important high added values, as important organic chemical industry's products such as pyrrolidones, N-methyl pyrrolidone, N-vinyl pyrrolidones.
The process route of synthetic gamma butyrolactone is a lot, be divided into furfural method, allyl alcohol method, butadiene chloridising, butadiene acetoxylation method, acrylate method, oxolane method, butynediols heating, thunder popularize law, 1 by raw material, 4-butanediol dehydrogenation method and maleic anhydride hydrogenation method etc., that wherein realizes suitability for industrialized production only has 1, two kinds of 4-butanediol dehydrogenation method and maleic anhydride hydrogenation methods.
Large-scale industrial production along with preparing cis-anhydride by n-butane oxidation technology, and in recent years because the employing of large-scale fluidized bed and mobile oxidation technology, greatly reduce the cis-butenedioic anhydride production cost, make cis-anhydride normal pressure hydrogenation preparing gama-butalactone technology more and more have competitiveness.
The catalyst of maleic anhydride hydrogenation system gamma-butyrolacton employing at present roughly can be divided three classes: noble metal catalyst, Ni series catalysts and Cu series catalysts, wherein the Cu series catalysts is the domestic and international research focus, and some Cu series catalysts has been realized suitability for industrialized production.
Chinese patent CN1058400A discloses a kind of method of ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride, and with cis-butenedioic anhydride or succinyl oxide, or their mixture is raw material, and the gas phase sample introduction carries out catalytic hydrogenation under condition of normal pressure, and catalyst is by Cu, ZnO, Al
2O
3Reach at least a the mixing in Ni, Ru, four kinds of elements of Ce, Zr, reaction temperature is 200～350 ℃, hydrogen: the mol ratio of cis-butenedioic anhydride is 5: 1～200: 1.The cis-butenedioic anhydride conversion per pass is near 100%, and the selectivity of gamma-butyrolacton and oxolane reaches 95%.
Chinese patent CN1071421A discloses a kind of catalyst that is used for gas phase cis-butenedioic anhydride or gas phase succinyl oxide are prepared oxolane and gamma-butyrolacton.It is carrier that this catalyst adopts the material with part hole of inertia, and the oxide-coated that will have catalytic activity is on the outer surface of carrier.The catalytic activity oxide is the oxide mixture of Cu, Zn and Al.
Chinese patent CN1108253A discloses the method that a kind of cis-butenedioic anhydride gas phase catalytic hydrogenation is produced gamma-butyrolacton, and catalyst is an inferior chromium-copper of going back ortho states, and it basic composition is CuO, Cr
2O
3And SiO
2CuO: Cr
2O
3: SiO
2Optimal proportion be about 78: 20: 2.
Chinese patent CN1111167A discloses a kind of catalyst of cis-butenedioic anhydride hydrogenation preparing gama-butalactone, by CuO, ZnO, Al
2O
3Form with the 4th component Pd or Pt.With CuO, ZnO and Al
2O
3Be parent, the 4th component is sprayed on the parent surface.The composition of unreduced catalyst Precursors (percentage by weight) is: CuO 20～65%, ZnO 20～55%, Al
2O
3The weight ratio of the 5～30%, the 4th component and parent is 0.005～0.1%.In 280 ℃ of reaction temperatures, normal pressure, hydrogen acid anhydride mol ratio is under 40 conditions, and the cis-butenedioic anhydride conversion ratio is 100%, and the gamma-butyrolacton selectivity is 92.7%.
It is the method that the raw material gas-phase catalytic hydrogenation prepares gamma-butyrolacton with cis-butenedioic anhydride or succinyl oxide that Chinese patent CN1139106A discloses a kind of, is with raw material cis-butenedioic anhydride and C
1～C
4Saturated monohydroxy alcohol according to the vaporization of the formed solution of 1: 1～4 mol ratio after, be 50～300 in hydrogen/acid anhydride mol ratio, temperature is that 200～300 ℃, pressure are that the liquid hourly space velocity (LHSV) of 0.1～2.0 MPa, raw material cis-butenedioic anhydride is 0.04～0.30h
-1Condition under, contact with the Cu-Zn-Cr-Zr catalyst of going back ortho states.This method can obtain near the gamma-butyrolacton selectivity more than 100% the cis-butenedioic anhydride conversion ratio and 85% under high-speed.
Chinese patent CN1298759A discloses a kind of preparing gamma-butyrolactone from cis-aldehyde by ordinary-pressure gas-phase hydrogenation catalyst and uses thereof, and the each component percentage by weight of catalyst is: CuO6～70%, ZnO15～40%; Al
2O
32～24%, auxiliary agent 0.001～10%, and wherein auxiliary agent is at least a in two kinds of materials of BaO, Pd.Cis-butenedioic anhydride steam and hydrogen mix the back by fixed bed reactors, and reaction temperature is 250～320 ℃, and reaction pressure is less than 0.05MPa, hydrogen and cis-butenedioic anhydride mol ratio 10～200, and cis-butenedioic anhydride liquid weight air speed is 0.02～0.26h
-1, the cis-butenedioic anhydride conversion per pass is 100%, the gamma-butyrolacton selectivity can reach 93～98%.
Chinese patent CN1314208A discloses a kind of Catalysts and its preparation method for preparing gamma-butyrolacton, and the percentage by weight of this catalyst consists of: Pd1.0～5.0%, Co1.0～5.0%, Ti0.5～10.0%, active carbon 84.0～95.0%.Adopt the step impregnation method to make, promptly the first step is impregnated into the precursor of Ti on the absorbent charcoal carrier in required ratio earlier, 120 ℃ of oven dry, again under nitrogen protection, in 400～600 roastings, 2～6h; Second step was immersed in the precursor of Pd and Co on the catalyst that the first step makes in required ratio, in 120 oven dry, under nitrogen protection, in 400～600 ℃ of roasting 2～6h, promptly got catalyst again.When this catalyst was used for maleic anhydride hydrogenation system gamma-butyrolacton, the gamma-butyrolacton selectivity was greater than 98%.
Chinese patent CN1358568A discloses a kind of Catalysts and its preparation method of cis-anhydride normal pressure hydrogenation preparing gama-butalactone.This catalyst is the catalyst of the cis-anhydride normal pressure hydrogenation system gamma-butyrolacton of a kind of Cu of containing, Zn, Al, does not add the 4th active component, and constituent content (wt%) is respectively: CuO10～80%, ZnO20～5%, Al
2O
31～40%, prepare with coprecipitation.
U.S. Pat 3065243 discloses a kind of in the presence of the Cu-Cr catalyst, be the method for raw material hydrogenation preparing gama-butalactone with cis-butenedioic anhydride, succinyl oxide, corresponding acid or ester, but cis-butenedioic anhydride conversion ratio and gamma-butyrolacton selectivity is quite low.
U.S. Pat 5347021 discloses a kind of catalyst of cis-butenedioic anhydride hydrogenation preparing gama-butalactone, and (percentage by weight of composition is: CuO50～60%, ZnO18～50%, Al
2O
38～22%, graphite 0～5%), at cis-butenedioic anhydride liquid hourly space velocity (LHSV) 0.05～0.25h
-1Under the condition, cis-butenedioic anhydride conversion ratio 100%, the gamma-butyrolacton selectivity is greater than 80%.
It is the method that the raw material gas-phase catalytic hydrogenation prepares gamma-butyrolacton with cis-butenedioic anhydride or succinyl oxide that U.S. Pat 6492535B1 discloses a kind of, catalyst consist of (wt%): CuO30～80%, Cr
2O
320～70%, BaO or MgO＜1% can obtain 100% cis-butenedioic anhydride conversion ratio and 92% above gamma-butyrolacton selectivity.
Though above-mentioned existing patented technology respectively has its characteristics, its weak point is also respectively arranged, for example: reaction temperature is higher, the raw material air speed is less, the gamma-butyrolacton selectivity is not high and catalyst contains poisonous component Cr element etc.
Summary of the invention
The object of the present invention is to provide a kind of being applicable under the high-speed condition, the cis-anhydride normal pressure gas phase hydrogenation with high activity, high selectivity prepares the Catalysts and its preparation method that gamma-butyrolacton is used.
The composition of catalyst of the present invention and weight percent content are:
CuO 5～60％，
TiO
2 10～50％，
Al
2O
3 29～75％，
Auxiliary agent 0.01～5%.
Wherein auxiliary agent is selected from a kind of or its mixture in the oxide of Mg, Ba, Zn, Sn, La or Ni.
Preferred composition and weight percent content are:
CuO 8～50％，
TiO
2 15～50％，
Al
2O
3 34～70％，
Auxiliary agent 0.05～5%.
Catalyst of the present invention can adopt coprecipitation or microemulsion method preparation.
Said coprecipitation comprises the steps:
Nitrate, tetrabutyl titanate or titanium sulfate and Mg, Ba, Zn, La, the nitrate of Ni or at least a soluble-salt in the stannous chloride with Cu and Al, be dissolved in absolute ethyl alcohol or the deionized water, add precipitating reagent, precipitation temperature is 25～60 ℃, and the solution endpoint pH is 5～9, after precipitation process finishes, ageing 0.5～12h filters then, washs, at 100～120 ℃ of down dry 8～24h, at 350～700 ℃ of following roasting 5～15h, last compression molding is stand-by.
Said precipitating reagent is Na
2CO
3, NaHCO
3, NaOH, K
2CO
3, KHCO
3, KOH, (NH
4)
2CO
3, NH
4HCO
3, in the ammoniacal liquor one or more.
Said microemulsion method comprises the steps:
Nitrate with Cu, Al, titanium sulfate, at least a soluble-salt in the nitrate of Mg, Ba, Zn, La, Ni or the stannous chloride is dissolved in the deionized water, be sequentially added into cyclohexane, Qu Latong and n-hexyl alcohol, form near transparent stable salt microemulsion (I);
Precipitating reagent is dissolved in the deionized water, is sequentially added into cyclohexane, Qu Latong and n-hexyl alcohol, form the microemulsion (II) of alkaline precipitating agent;
Precipitating reagent is selected from Na
2CO
3, NaHCO
3, NaOH, K
2CO
3, KHCO
3, KOH, (NH
4)
2CO
3, NH
4HCO
3, in the ammoniacal liquor one or more;
The volume ratio of Qu Latong, n-hexyl alcohol and cyclohexane is: Qu Latong/n-hexyl alcohol/cyclohexane=1/1～3/7～10;
The volume ratio of water and cyclohexane is: water/cyclohexane=1/1～8;
Under the vigorous stirring state, slowly be added drop-wise in the salt microemulsion (II) in 25～60 ℃ of microemulsions (I) alkaline precipitating agent, control solution endpoint pH is 5～9;
After precipitation process finished, ageing 0.5～12h filtered then, washs, and at 100～120 ℃ of down dry 8～24h, at 350～700 ℃ of following roasting 5～15h, last compression molding is stand-by.
Before use, catalyst will carry out reduction activation, and active condition is:
Hydrogen with hydrogen or nitrogen dilution activates catalyst, under 0.1～0.5MPa pressure, carries out in-situ reducing 5～30h in 150～400 ℃ in fixed bed reactors, till reactor outlet end dry-steam.
Be used for the cis-anhydride normal pressure gas phase hydrogenation through the catalyst of overactivation and prepare the gamma-butyrolacton reaction, its reaction condition is: 160～350 ℃ of reaction temperatures, value preferably are 180～300 ℃, reaction pressure 0.1～0.5MPa, cis-butenedioic anhydride liquid hourly space velocity (LHSV) 0.02～1.5h
-1, value preferably is 0.1～1.0h
-1, hydrogen/cis-butenedioic anhydride mol ratio 2～200.Cis-butenedioic anhydride conversion ratio and gamma-butyrolacton selectivity all can reach 100% respectively.Even along with the reaction carrying out, catalyst activity constantly descends, but to the selectivity of GBL still can maintain～100%.Behind the catalyst carbon deposit inactivation, can use the air coke-burning regeneration.
One of remarkable advantage of catalyst of the present invention is that the catalyst activity component is at least a the mixing in Cu, Ti, Al and Mg, Ba, Zn, Sn, La, six kinds of elements of Ni, does not contain poisonous component Cr element, belongs to the catalyst of environment-friendly type.
Two of the remarkable advantage of catalyst of the present invention is, catalyst can use under high cis-butenedioic anhydride liquid hourly space velocity (LHSV), have higher cis-butenedioic anhydride conversion ratio and gamma-butyrolacton selectivity, can reach 100% respectively, even carrying out along with reaction, catalyst activity constantly descends, but to the selectivity of GBL maintain all the time～100%, this separation to product is very favourable.
Three of the remarkable advantage of catalyst of the present invention is, because catalyst has excellent catalytic performance, and gamma-butyrolacton once through yield height, operating procedure is simple, is the higher cis-anhydride normal pressure hydrogenation preparing gama-butalactone catalyst of a kind of cost performance.
The specific embodiment
Embodiment 1
(CuO 12%, TiO according to the proportion of composing (wt%) of catalyst
225%, Al
2O
360%, BaO 3%), with 3.64 gram Cu (NO
3)
23H
2O, 10.7ml tetrabutyl titanate, 44.1 gram Al (NO
3)
39H
2O, 0.5 gram Ba (NO
3)
2Be dissolved in the 250ml absolute ethyl alcohol, in 40, slowly drip saturated aqueous sodium carbonate under the high-speed stirred condition, control solution endpoint pH is 8～9.After precipitation process finished, ageing 6h filtered then, washs, at 120 ℃ of dry 12h, and 550 ℃ of roasting 7h, last compression molding is stand-by.
20～40 order catalyst of 6ml are loaded in the fixed bed reactors of Φ 10mm,, feed 8% H then at 300 ℃
2/ N
2Mixed gas carries out the in-situ reducing activation, till reactor outlet end dry-steam produces.
180～270 ℃ of reaction temperatures, normal pressure, cis-butenedioic anhydride liquid hourly space velocity (LHSV) 0.4h
-1, hydrogen/cis-butenedioic anhydride mol ratio is to carry out catalyst performance evaluation under 50 the condition, cis-butenedioic anhydride conversion ratio and gamma-butyrolacton selectivity all can reach 100%.
Embodiment 2
Proportion of composing (wt%) (CuO12%, TiO according to catalyst
225%, Al
2O
360%, BaO3%), with 3.64 gram Cu (NO
3)
23H
2O, 12.6 gram Ti (SO
4)
29H
2O, 44.1 gram Al (NO
3)
39H
2O, 0.5 gram Ba (NO
3)
2Be dissolved in the 180ml deionized water, under the vigorous stirring state, be sequentially added into 1100ml cyclohexane, 150ml song and draw logical and 180ml n-hexyl alcohol, form near transparent stable salt microemulsion.Prepare the microemulsion of alkaline precipitating agent sodium carbonate again with same procedure.In 40 ℃, the sodium carbonate microemulsion slowly is added drop-wise in the microemulsion of salt under the vigorous stirring state, control solution endpoint pH is 8～9.After precipitation process finished, ageing 12h filtered then, washs, at 120 ℃ of dry 12h, and 550 ℃ of roasting 7h, last compression molding is stand-by.
All the other conditions are identical with embodiment 1, and cis-butenedioic anhydride conversion ratio and gamma-butyrolacton selectivity all can reach 100%.
Embodiment 3
Proportion of composing (wt%) (CuO50%, TiO according to catalyst
215%, Al
2O
334%, La
2O
31%), with 15.2 gram Cu (NO
3)
23H
2O, 6.4ml tetrabutyl titanate, 25.0 gram Al (NO
3)
39H
2O, 0.3 gram La (NO
3)
36H
2O is dissolved in the 250ml absolute ethyl alcohol, in 40 ℃, slowly drips saturated aqueous sodium carbonate under the high-speed stirred condition, and control solution endpoint pH is 8～9.After precipitation process finished, ageing 6h filtered then, washs, at 120 dry 12h, and 550 ℃ of roasting 7h, last compression molding is stand-by.
All the other conditions are identical with embodiment 1, and the cis-butenedioic anhydride conversion ratio is greater than 95%, and the gamma-butyrolacton selectivity is greater than 90%.
Embodiment 4
Proportion of composing (wt%) (CuO24%, TiO according to catalyst
235%, Al
2O
339%, La
2O
32%), with 7.3 gram Cu (NO
3)
23H
2O, 17.6 gram Ti (SO
4)
29H
2O, 28.7 gram Al (NO
3)
39H
2O, 0.5 gram La (NO
3)
36H
2O is dissolved in the 180ml deionized water, is sequentially added into 1100ml cyclohexane, 150ml song and draws logical and 180ml n-hexyl alcohol under the vigorous stirring state, forms near transparent stable salt microemulsion.Prepare the microemulsion of alkaline precipitating agent sodium carbonate again with same procedure.In 40 ℃, the sodium carbonate microemulsion slowly is added drop-wise in the microemulsion of salt under the vigorous stirring state, control solution endpoint pH is 8～9.After precipitation process finished, ageing 12h filtered then, washs, at 120 ℃ of dry 12h, and 550 ℃ of roasting 7h, last compression molding is stand-by.
All the other conditions are identical with embodiment 1, and the cis-butenedioic anhydride conversion ratio is greater than 95%, and the gamma-butyrolacton selectivity is greater than 90%.
Claims (7)
1. a cis-anhydride normal pressure hydrogenation preparing gama-butalactone catalyst is characterized in that, the component of described catalyst and weight percent content thereof are:
CuO 5～60％，
TiO
2 10～50％，
Al
2O
3 29～75％，
Auxiliary agent 0.01～5%,
Wherein auxiliary agent is selected from a kind of or its mixture in the oxide of Mg, Ba, Sn or La.
2. catalyst according to claim 1 is characterized in that, the component of described catalyst and weight percent content thereof are:
CuO 8～50％，
TiO
2 15～50％，
Al
2O
3 34～70％，
Auxiliary agent 0.05～5%.
3. catalyst according to claim 1 and 2 is characterized in that, the catalytic reaction condition of cis-anhydride normal pressure hydrogenation preparing gama-butalactone is: 160～350 ℃ of reaction temperatures, reaction pressure 0.1～0.5MPa, cis-butenedioic anhydride liquid hourly space velocity (LHSV) 0.02～1.5h
-1, hydrogen/cis-butenedioic anhydride mol ratio 2～200.
4. catalyst according to claim 3 is characterized in that, described catalytic reaction condition is: 180～300 ℃ of reaction temperatures, reaction pressure 0.1～0.5MPa, cis-butenedioic anhydride liquid hourly space velocity (LHSV) 0.1～1.0h
-1, hydrogen/cis-butenedioic anhydride mol ratio 2～200.
5. prepare the method for claim 1 or 2 described catalyst, it is characterized in that, be coprecipitation, comprise the steps:
With the nitrate of copper, the nitrate of aluminium, tetrabutyl titanate or titanium sulfate, at least a soluble-salt in four kinds of the nitrate of the nitrate of magnesium, the nitrate of barium, lanthanum or the stannous chlorides, be dissolved in absolute ethyl alcohol or the deionized water, add precipitating reagent then, the control precipitation temperature is at 25～60 ℃, control solution endpoint pH is 5～9, after precipitation process finished, ageing 0.5～12h filtered then, washs, at 100～120 ℃ of down dry 8～24h, at 350～700 ℃ of following roasting 5～15h;
Said precipitating reagent is Na
2CO
3, NaHCO
3, NaOH, K
2CO
3, KHCO
3, KOH, (NH
4)
2CO
3, NH
4HCO
3, in the ammoniacal liquor one or more.
6. prepare the method for claim 1 or 2 described catalyst, it is characterized in that, be microemulsion method, comprise the steps:
With the nitrate of copper, the nitrate of aluminium, titanium sulfate, at least a soluble-salt in four kinds of the nitrate of the nitrate of magnesium, the nitrate of barium, lanthanum or the stannous chlorides, be dissolved in the deionized water, be sequentially added into cyclohexane, Qu Latong and n-hexyl alcohol, form salt microemulsion (I);
Precipitating reagent is dissolved in the deionized water, is sequentially added into cyclohexane, Qu Latong and n-hexyl alcohol, form the microemulsion (II) of alkaline precipitating agent;
Said precipitating reagent is selected from Na
2CO
3, NaHCO
3, NaOH, K
2CO
3, KHCO
3, KOH, (NH
4)
2CO
3, NH
4HCO
3, in the ammoniacal liquor one or more;
The volume ratio of Qu Latong, n-hexyl alcohol and cyclohexane is: Qu Latong/n-hexyl alcohol/cyclohexane=1/1～3/7～10;
The volume ratio of deionized water and cyclohexane is: deionized water/cyclohexane=1/1～8;
The microemulsion (II) of alkaline precipitating agent is joined in the salt microemulsion (I), and the control precipitation temperature is at 25～60 ℃, and control solution endpoint pH is 5～9;
After precipitation process finished, ageing 0.5～12h filtered then, washs, at 100～120 ℃ of down dry 8～24h, at 350～700 ℃ of following roasting 5～15h.
7. the activation method of catalyst according to claim 1 and 2, it is characterized in that, hydrogen with hydrogen or nitrogen dilution activates catalyst, under 0.1～0.5MPa pressure, in fixed bed reactors, carry out in-situ reducing 5～30h in 150～400 ℃, till reactor outlet end dry-steam.
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| CN102188978A (en) * | 2011-03-28 | 2011-09-21 | 广州大学 | Catalyst for preparing gamma-butyrolactone by gas-phase hydrogenation of maleic-anhydride |
| CN102228834A (en) * | 2011-04-19 | 2011-11-02 | 常州大学 | Catalyst for catalytic hydrogenation and application thereof |
| CN103880787B (en) * | 2014-03-12 | 2016-08-24 | 江苏大学 | A kind of coupled reaction prepares the method for gamma-butyrolacton and acetone |
| CN110898841B (en) * | 2018-09-18 | 2022-09-13 | 中国石油化工股份有限公司 | Cyclohexanone light oil hydrogenation catalyst and application thereof |
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