CN103566939A - Catalyst for preparing gamma-butyrolactone through normal-pressure gas-phase hydrogenation of maleic anhydride and preparation method and application thereof - Google Patents
Catalyst for preparing gamma-butyrolactone through normal-pressure gas-phase hydrogenation of maleic anhydride and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing gamma-butyrolactone through normal-pressure gas-phase hydrogenation of maleic anhydride and a preparation method and application thereof. The catalyst disclosed by the invention is prepared by a suspension coprecipitation process and consists of a blend of an active component CuO, an auxiliary ZnO, a carrier Al2O3 and active carbon, and specifically consists of 15-35wt% of CuO, 15-35wt% of ZnO, 15-35wt% of Al2O3 and 2-10wt% of active carbon. Without a toxic component, the catalyst disclosed by the invention belongs to a green catalyst. Under a high liquid hourly space velocity of maleic anhydride, the catalyst has a maleic anhydride conversion rate as high as 100% and gamma-butyrolactone selectivity over 95% as well as catalysis stability. The catalyst disclosed by the invention has excellent catalysis performance, does not contain precious metal, and is a catalyst for gas-phase hydrogenation of maleic anhydride, with relatively high cost performance.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and purposes of cis-anhydride normal pressure hydrogenation preparing gama-butalactone, relate to particularly a kind of by CuO, ZnO, Al
2o
3catalyst with active carbon composition.
Background technology
Gamma-butyrolacton is a kind of pentacyclic heterocyclic compound that contains, and has high boiling point and high solvability, and reactivity worth is good, and electrical conductivity is high, and good stability is used safety.Gamma-butyrolacton can dissolve various organic and inorganic compounds, is commonly used for solvent, extractant and absorbent.Can there is the chemical reaction of a series of open loop and not open loop in good reactivity worth, can be used for Ciprofloxacin, piracetam, Cobastab
1, PVP etc. raw materials for production, wherein pyrrolidones can be used to produce the adhesive of latex, the organic solvent of the NMF of cosmetics and polymer etc. in nylon monomer, plasticizer, floor wax.The dissolubility that it is stable and electrolyte, make its special solvent that can be used as high conductivity for the electrolyte of lithium battery and electrical equipment.Gamma-butyrolacton and derivative thereof can be widely used in the industrial circles such as petrochemical industry, weaving, spices, agricultural chemicals and medicine.
The synthesis technique of gamma-butyrolacton is a lot, but realize, industrializedly mainly contains 3 kinds: 1. take the Reppe method that acetylene and formaldehyde is raw material; 2. the furfural hydrogenation method that the acetoxylation method that the butadiene of take is raw material and the agricultural production waste material of take are raw material; 3. the maleic anhydride hydrogenation method that the cis-butenedioic anhydride of take is raw material.
At present, the catalyst that maleic anhydride hydrogenation gamma-butyrolacton processed adopts roughly can be divided three classes: noble metal catalyst, Ni series catalysts and Cu series catalysts, wherein Cu-Zn series catalysts is study hotspot both domestic and external.
Chinese patent CN1058400A discloses a kind of by Cu, ZnO, Al
2o
3, and at least one catalyst mixing in Ni, Ru, Ce, tetra-kinds of elements of Zr, cis-butenedioic anhydride conversion per pass approaches 100%, gamma-butyrolacton and oxolane selectively reach 95%, but the one way of this catalyst is lower service life.
Chinese patent CN1111167A discloses a kind of by CuO, ZnO, Al
2o
3catalyst with the 4th component Pd or Pt composition.With CuO, ZnO and Al
2o
3for parent, the 4th component is sprayed on parent surface, and the cis-butenedioic anhydride conversion ratio of this catalyst is 100%, and gamma-butyrolacton is selectively 92.7%.
Chinese patent CN1139106A discloses a kind of by CuO, ZnO, Cr
2o
3, ZrO
2the catalyst forming.The gamma-butyrolacton that the method can obtain more than the cis-butenedioic anhydride conversion ratio and 85% that approaches 100% under high-speed is selective.
Chinese patent CN1071421A discloses a kind of catalyst being comprised of Cu/Zn/Al/O.It is carrier that this catalyst adopts the material with part hole of inertia, by the oxide-coated with catalytic activity on the outer surface of carrier.
Chinese patent CN1298759A discloses a kind of by CuO, ZnO, Al
2o
3, auxiliary agent (BaO or Pd).Cis-butenedioic anhydride conversion per pass is 100%, and gamma-butyrolacton selectively can reach 93～98%.
Chinese patent CN1108253A discloses the sub-chromium-copper that a kind of catalyst is reduction-state, and it basic composition is CuO, Cr
2o
3and SiO
2, reaction effect is better, but contains heavy metal Cr in this catalyst.The existence of Cr easily causes environmental pollution, enters Cr VI in human body and gathers for a long time, is difficult to by metabolism, very large to human health damage.
Chinese patent CN1358568A discloses the catalyst of a kind of Cu of containing, Zn, Al, does not add the 4th active component, by coprecipitation, prepares.
Chinese patent CN1314208A discloses a kind of catalyst being comprised of Pd, Co and active carbon.Adopt step impregnation method to make, gamma-butyrolacton is selectively greater than 98%.
Chinese patent CN1669651A discloses a kind of by CuO, TiO
2, Al
2o
3and the catalyst that forms of auxiliary agent (being selected from a kind of or its mixture in the oxide of Mg, Ba, Zn, Sn, La or Ni).Cis-butenedioic anhydride conversion ratio 100%, gamma-butyrolacton is selective 100%, but carrying out gamma-butyrolacton and selectively will decline gradually along with reaction.
Chinese patent CN1646514 discloses and a kind ofly by CuO and at least one, has been selected from the catalyst of silica, titanium dioxide, hafnium oxide, magnesium silicate, active carbon, carborundum, zirconium dioxide and aluminium oxide.The gamma-butyrolacton productive rate obtaining at 245-270 ℃ is only 94.9～96.6%.
US Patent No. 6492535B1 discloses a kind of by CuO, Cr
2o
3, BaO or MgO, cis-butenedioic anhydride conversion ratio 100% and gamma-butyrolacton selective more than 92%.
US Patent No. 5347021 discloses a kind of CuO, ZnO, Al
2o
3catalyst with trace graphite composition.Cis-butenedioic anhydride conversion ratio 100%, gamma-butyrolacton is only selectively 80%.
Although the disclosed catalyst of above-mentioned patent differs from one another, still there is selectively not high, the shortcoming such as reaction temperature is higher, raw material air speed is lower, catalyst activity is unstable, service life is shorter, cost of manufacture is higher of gamma-butyrolacton.Therefore, develop there is higher activity, the catalyst of the preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation of selective and stability has realistic meaning.
Summary of the invention
The object of this invention is to provide a kind of green catalyst that does not contain precious metal or poisonous component, there is industrial application value, it is prepared in the reaction of gamma-butyrolacton at cis-butenedioic anhydride gas-phase catalytic hydrogenation, under high cis-butenedioic anhydride liquid hourly space velocity (LHSV), there is high cis-butenedioic anhydride conversion ratio, gamma-butyrolacton high selectivity and catalytic stability.
Another object of the present invention is to provide a kind of preparation method of aforementioned catalyst.
Another object of the present invention is to provide a kind of aforementioned catalyst and prepares the application in gamma-butyrolacton at catalytic hydrogenation cis-butenedioic anhydride.
To achieve these goals, the present invention adopts following technical scheme:
A catalyst for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation, is characterized in that described catalyst is by CuO, ZnO, Al
2o
3form with active carbon, the weight percent content of each component is: CuO10～40%, ZnO10～40%, Al
2o
310～40%, active carbon 1～25%.
In a preferred embodiment, the weight percent content of described each component is: CuO15～35%, ZnO15～35%, Al
2o
315～35%, active carbon 2～10%.
The preparation method of catalyst, adopt suspension coprecipitation, active carbon is suspended in deionized water, add the nitrate of Cu, Zn and Al, wherein Cu (NO
3)
23H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o and active carbon weight ratio are Cu (NO
3)
23H
2o: Zn (NO
3)
26H
2o: Al (NO
3)
39H
2o: active carbon=35～45: 35～45: 45～55: 1.5～12; At 60～80 ℃, stir 1～4h, then add precipitating reagent, control precipitation temperature at 60～80 ℃, controlling pH is 6～8, after precipitation process finishes, ageing 12～24h, then filter, wash, dry 8～12h at 80～130 ℃, roasting 3～4h at 300～400 ℃, compression molding, fragmentation.
Wherein, described active carbon is 100～200 orders.
Wherein, described precipitating reagent is Na
2cO
3, NaHCO
3, NaOH, K
2cO
3, KHCO
3, KOH, (NH
4)
2cO
3, NH
4hCO
3, one or more in ammoniacal liquor.Preferably, described precipitating reagent is Na
2cO
3.
Wherein, described catalyst breakage to 20～40 order granular size.
Wherein, described Cu (NO
3)
23H
2o: Zn (NO
3)
26H
2o: Al (NO
3)
39H
2o: active carbon=40: 40: 50: 1.5～12.
A kind of catalyst hydrogenation cis-butenedioic anhydride of preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation is prepared the application of gamma-butyrolacton, after comprising that cis-butenedioic anhydride steam and hydrogen mix, gaseous phase materials is by being equipped with the step of the fixed bed of catalyst, it is characterized in that described catalytic reaction condition is: 270～300 ℃ of reaction temperatures, reaction pressure 0.1～0.15MPa, cis-butenedioic anhydride liquid hourly space velocity (LHSV) 0.1～0.5h
-1, hydrogen and cis-butenedioic anhydride mol ratio 20: 1～200: 1.
In a preferred embodiment, before described catalytic reaction, also comprise the activation step of catalyst, adopt the hydrogen of nitrogen dilution to activate catalyst, under 0.1～0.5MPa pressure, in 270～300 ℃, in fixed bed reactors, carry out in-situ reducing, until reactor outlet end dry-steam.
Catalyst of the present invention has the following advantages: (1) catalyst can be used under high cis-butenedioic anhydride liquid hourly space velocity (LHSV), and cis-butenedioic anhydride liquid air speed reaches 0.1～0.5h
-1, hydrogen acid anhydride mol ratio reaches 20: 1～and 200: 1.(2) catalyst can be used under high cis-butenedioic anhydride liquid hourly space velocity (LHSV), has the cis-butenedioic anhydride conversion ratio up to 100%, and gamma-butyrolacton selectively reaches more than 95%.(3) in reaction production fluid, only have micro-accessory substance n-butanol to generate, this is very favourable to the separation of product.(4) to take activated centre Cu, auxiliary agent ZnO, carrier be Al to catalyst
2o
3/ active carbon mixes, and or not containing poisonous component Cr element, does not belong to green catalyst.(5) catalyst adopts active carbon as carrier, greatly reduces the proportion of catalyst.(6) catalyst is not containing noble metal component Pt, Pd etc., and manufacture craft is simple, with low cost, is the cis-anhydride normal pressure hydrogenation preparing gama-butalactone catalyst that a kind of cost performance is higher.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is done to further expansion explanation, but it is pointed out that Catalysts and its preparation method of the present invention and purposes are not limited to this concrete composition and preparation method.Obviously be understandable that for those skilled in the art, even if the following description content does not make any adjustments or revises, also can be directly applied in these unspecified other similar preparation method and application.
A catalyst for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation, described catalyst is by CuO, ZnO, Al
2o
3form with active carbon, the weight percent content of each component is: CuO10～40%, ZnO10～40%, Al
2o
310～40%, active carbon 1～25%; CuO15～35% preferably, ZnO15～35%, Al
2o
315～35%, active carbon 2～10%.This catalyst is after the activation step before reaction, and CuO is activated as active component Cu, and ZnO is as auxiliary agent, Al
2o
3with active carbon blend be the carrier of aforementioned active component and auxiliary agent, wherein the granular size of active carbon is that 100～200 orders are better.In catalyst, the purity of each component, without any restriction, can be carried out corresponding selection according to the requirement of catalytic hydrogenation, for example, be technical pure, but be not limited to this.
The preparation method of catalyst, adopt suspension coprecipitation, active carbon is suspended in deionized water, add the nitrate of Cu, Zn and Al, wherein Cu (NO
3)
23H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o and active carbon weight ratio are Cu (NO
3)
23H
2o: Zn (NO
3)
26H
2o: Al (NO
3)
39H
2o: active carbon=35～45: 35～45: 45～55: 1.5～12, be preferably described Cu (NO
3)
23H
2o: Zn (NO
3)
26H
2o: Al (NO
3)
39H
2o: active carbon=40: 40: 50: 1.5～12.; At 60～80 ℃, stir 1～4h, then add precipitating reagent, control precipitation temperature at 60～80 ℃, controlling pH is 6～8, after precipitation process finishes, ageing 12～24h, then filter, wash, dry 8～12h at 80～130 ℃, roasting 3～4h at 300～400 ℃, compression molding, fragmentation.
The suspension coprecipitation that the preparation of described catalyst adopts is prior art, and stirring wherein, filtration, washing, be dried etc. is conventional means, and compression molding wherein and fragmentation, can be with reference to the processing mode of existing copper series catalysts.Described precipitating reagent is Na
2cO
3, NaHCO
3, NaOH, K
2cO
3, KHCO
3, KOH, (NH
4)
2cO
3, NH
4hCO
3, one or more in ammoniacal liquor.Preferably, described precipitating reagent is Na
2cO
3, anhydrous Na
2cO
3better.Other precipitating reagents have or not the crystallization water without any restriction, as long as contain corresponding precipitating reagent composition.Precipitating reagent add form without any restriction, for example can slowly add the powder of precipitating reagent, or add certain density precipitating reagent reagent, be generally and regulate more easily pH value, first precipitating reagent is dissolved, then with the form of the precipitating reagent aqueous solution, add goodly, but be not limited to this.
The preparation of described catalyst adopts suspension coprecipitation, wherein adds the soluble salt that contains Cu, Zn and Al, is not limited to nitrate, it can also be for example hydrochloride, as long as it is CuO10～40% that the product weight adding finally can meet the weight percent content of each component, ZnO10～40%, Al
2o
310～40%, active carbon 1～25%.
Described catalyst is prepared gamma-butyrolacton for catalytic hydrogenation cis-butenedioic anhydride, after comprising that cis-butenedioic anhydride steam and hydrogen mix, gaseous phase materials carries out the step of catalytic hydrogenation by the fixed bed reactors of catalyst are housed, fixed-bed catalytic hydrogenation reactor and feeding manner, mode of heating are same as the prior art, different is to utilize the catalytic reaction condition of catalyst of the present invention to be: 270～300 ℃ of reaction temperatures, reaction pressure 0.1～0.15MPa, cis-butenedioic anhydride liquid hourly space velocity (LHSV) 0.1～0.5h
-1, hydrogen and cis-butenedioic anhydride mol ratio 20: 1～200: 1.
It should be noted that, before described catalytic reaction, preferably to carry out the activation of catalyst, activation method is for adopting the hydrogen of nitrogen dilution to activate catalyst, under 0.1～0.5MPa pressure, in 270～300 ℃, in fixed bed reactors, carry out in-situ reducing, until reactor outlet end dry-steam.By activation, by the CuO activating and reducing in catalytic component, be active component Cu, thereby improve the catalytic activity of catalyst.
In the present invention, not specified term is the general technical term in this area, is applicable to those skilled in the art's general understanding.Below by embodiment more specifically, describe Catalysts and its preparation method of the present invention and purposes, what deserves to be explained is, these embodiment only play example effect, the present invention are not had to any restriction.
Embodiment 1:
1. the preparation of catalyst
(1) by 1.50g active carbon powder (100 order), 39.77g Cu (NO
3)
23H
2o, 40.68g Zn (NO
3)
26H
2o, 51.00gAl (NO
3)
3.9H
2o is placed in the beaker that 1000ml deionized water is housed, and stirs 1 hour at 80 ℃, then slowly adds the Na of 0.5mol/L
2cO
3the aqueous solution, is uniformly mixed, until the pH value of system is that between 6～8 scopes, precipitation finishes.Standing 12～24 hours, filter, washing, at 110 ℃ dry 12 hours, roasting was 4 hours at 400 ℃, obtains catalyst fines 39.61g, and compression molding, is broken into 20 order particles standby.
2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and to catalyst components, divide quantitative analysis by the method for ICP-AES, analytical method is as follows:
Adopt the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, take AlK α as excitaton source, the resolution ratio of instrument is 1.15eV, after sample compressing tablet, is fixed on sample carrier and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company to analyze each constituent content.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, assisted gas flow 1.0L/min, atomization gas flow 0.8L/min.
The analysis result that this catalyst forms is 33.12wt%CuO, 28.09wt%ZnO, 35.00wt%Al
2o
3, 3.79wt%C.
3. cis-butenedioic anhydride catalytic hydrogenation reaction
A) catalyst granules obtaining in step 1 is inserted in the fixed bed reactors of φ 14mm to interior filling 20 order catalyst 6～8mL.H with 10%
2/ N
2mist activates catalyst at 0.2MPa, 300 ℃, until reactor outlet end is without the globule.
B) at 270 ℃, 0.15MPa, cis-butenedioic anhydride liquid air speed 0.15h
-1, under the hydrogen acid anhydride mol ratio condition of 50: 1, catalyst is evaluated.The cooling collection product of ice-water bath, adopts gas chromatographic analysis, and cis-butenedioic anhydride conversion ratio is 100%, and gamma-butyrolacton is selectively greater than 95%, and catalyst is used 2000 hours continuously, active not obviously reduction.
Embodiment 2:
1. the preparation of catalyst
(1) by 3.00g active carbon powder (135 order), 39.77g Cu (NO
3)
23H
2o, 40.68g Zn (NO
3)
26H
2o, 51.00g Al (NO
3)
3.9H
2o is placed in 1000ml ionized water beaker is housed, and stirs 1 hour at 80 ℃, then slowly adds the Na of 0.5mol/L
2cO
3the aqueous solution, is uniformly mixed, until the pH value of system is that within 6～8 scopes, precipitation finishes.Standing 12～24 hours, filter, washing, at 110 ℃ dry 12 hours, roasting was 4 hours at 400 ℃, obtains catalyst fines 41.11g, and compression molding, is broken into 25 order particles standby.
2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and to catalyst components, divide quantitative analysis by the method for ICP-AES, analytical method is as follows:
Adopt the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, take AlK α as excitaton source, the resolution ratio of instrument is 1.15eV, after sample compressing tablet, is fixed on sample carrier and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company to analyze each constituent content.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, assisted gas flow 1.0L/min, atomization gas flow 0.8L/min.
The analysis result that this catalyst forms is 31.91wt%CuO, 37.07wt%ZnO, 33.73wt%Al
2o
3, 7.30wt%C.
3. cis-butenedioic anhydride catalytic hydrogenation reaction
A) catalyst granules obtaining in step 1 is inserted in the fixed bed reactors of φ 14mm to interior filling 25 order catalyst 6～8mL.H with 10%
2/ N
2mist activates catalyst at 0.2MPa, 300 ℃, until reactor outlet end is without the globule.
B) at 270 ℃, 0.15MPa, cis-butenedioic anhydride liquid air speed 0.15h
-1, under the hydrogen acid anhydride mol ratio condition of 50: 1, catalyst is evaluated.The cooling collection product of ice-water bath, adopts gas chromatographic analysis, and cis-butenedioic anhydride conversion ratio is 100%, and gamma-butyrolacton is selectively greater than 95%, and catalyst is used 2000 hours continuously, active not obviously reduction.
Embodiment 3:
1. the preparation of catalyst
(1) by 6.00g active carbon powder (175 order), 39.77g Cu (NO
3)
23H
2o, 40.68g Zn (NO
3)
26H
2o, 51.00gAl (NO
3)
3.9H
2o is placed in 1000ml ionized water beaker is housed, and stirs 1 hour at 80 ℃, then slowly adds the Na of 0.5mol/L
2cO
3the aqueous solution, is uniformly mixed, until the pH value of system is that within 6～8 scopes, precipitation finishes.Standing 12～24 hours, filter, washing, at 110 ℃ dry 12 hours, roasting was 4 hours at 400 ℃, obtains catalyst fines 44.11g, and compression molding, is broken into 30 order particles standby.
2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and to catalyst components, divide quantitative analysis by the method for ICP-AES, analytical method is as follows:
Adopt the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, take AlK α as excitaton source, the resolution ratio of instrument is 1.15eV, after sample compressing tablet, is fixed on sample carrier and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company to analyze each constituent content.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, assisted gas flow 1.0L/min, atomization gas flow 0.8L/min.
The analysis result that this catalyst forms is 29.74wt%CuO, 25.23wt%ZnO, 31.43wt%Al
2o
3, 13.60wt%C.
3. cis-butenedioic anhydride catalytic hydrogenation reaction
A) catalyst granules obtaining in step 1 is inserted in the fixed bed reactors of φ 14mm to interior filling 30 order catalyst 6～8mL.H with 10%
2/ N
2mist activates catalyst at 0.2MPa, 300 ℃, until reactor outlet end is without the globule.
B) at 270 ℃, 0.15MPa, cis-butenedioic anhydride liquid air speed 0.15h
-1, under the hydrogen acid anhydride mol ratio condition of 50: 1, catalyst is evaluated.The cooling collection product of ice-water bath, adopts gas chromatographic analysis, and cis-butenedioic anhydride conversion ratio is 100%, and gamma-butyrolacton is selectively greater than 95%, and catalyst is used 2000 hours continuously, active not obviously reduction.
Embodiment 4:
1. the preparation of catalyst
(1) by 12.00g active carbon powder (200 order), 39.77g Cu (NO
3)
23H
2o, 40.68g Zn (NO
3)
26H
2o, 51.00gAl (NO
3)
3.9H
2o is placed in 1000ml ionized water beaker is housed, and stirs 1 hour at 80 ℃, then slowly adds the Na of 0.5mol/L
2cO
3the aqueous solution, is uniformly mixed, until the pH value of system is that within 6～8 scopes, precipitation finishes.Standing 12～24 hours, filter, washing, at 110 ℃ dry 12 hours, roasting was 4 hours at 400 ℃, obtains catalyst fines 50.11g, and compression molding, is broken into 40 order particles standby.
2. the composition of catalyst
Adopt XPS analysis catalyst surface atom valence state, and to catalyst components, divide quantitative analysis by the method for ICP-AES, analytical method is as follows:
Adopt the K-Alpha type x-ray photoelectron spectroscopy (XPS) of Thermofisher Scienticfic company, take AlK α as excitaton source, the resolution ratio of instrument is 1.15eV, after sample compressing tablet, is fixed on sample carrier and tests.
Adopt the OPTIMA-3300RL type inductively coupled plasma emission spectrometer of Perkin Elmer company to analyze each constituent content.Analysis condition: incident power 1400W, height of observation 12mm, plasma gas flow rate 15L/min, assisted gas flow 1.0L/min, atomization gas flow 0.8L/min.
The analysis result that this catalyst forms is 26.18wt%CuO, 22.21wt%ZnO, 27.67wt%Al
2o
3, 23.94wt%C.
3. cis-butenedioic anhydride catalytic hydrogenation reaction
A) catalyst granules obtaining in step 1 is inserted in the fixed bed reactors of φ 14mm to interior filling 40 order catalyst 6～8mL.H with 10%
2/ N
2mist activates catalyst at 0.2MPa, 300 ℃, until reactor outlet end is without the globule.
B) at 270 ℃, 0.15MPa, cis-butenedioic anhydride liquid air speed 0.15h
-1, under the hydrogen acid anhydride mol ratio condition of 50: 1, catalyst is evaluated.The cooling collection product of ice-water bath, adopts gas chromatographic analysis, and cis-butenedioic anhydride conversion ratio is 100%, and gamma-butyrolacton is selectively greater than 95%, and catalyst is used 2000 hours continuously, active not obviously reduction.
Embodiment 5:
With embodiment 1, different is at 280 ℃, 0.15MPa, cis-butenedioic anhydride liquid air speed 0.25h
-1, under the hydrogen acid anhydride mol ratio condition of 20: 1, catalyst is evaluated.The cooling collection product of ice-water bath, adopts gas chromatographic analysis, and cis-butenedioic anhydride conversion ratio is 100%, and gamma-butyrolacton is selectively greater than 95%, and catalyst is used 2000 hours continuously, active not obviously reduction.
Embodiment 6:
With embodiment 2, different is at 290 ℃, 0.15MPa, cis-butenedioic anhydride liquid air speed 0.35h
-1, under the hydrogen acid anhydride mol ratio condition of 100: 1, catalyst is evaluated.The cooling collection product of ice-water bath, adopts gas chromatographic analysis, and cis-butenedioic anhydride conversion ratio is 100%, and gamma-butyrolacton is selectively greater than 95%, and catalyst is used 2000 hours continuously, active not obviously reduction.
Embodiment 7:
With embodiment 3, different is at 300 ℃, 0.15MPa, cis-butenedioic anhydride liquid air speed 0.45h
-1, under the hydrogen acid anhydride mol ratio condition of 150: 1, catalyst is evaluated.The cooling collection product of ice-water bath, adopts gas chromatographic analysis, and cis-butenedioic anhydride conversion ratio is 100%, and gamma-butyrolacton is selectively greater than 95%, and catalyst is used 2000 hours continuously, active not obviously reduction.
Embodiment 8:
With embodiment 4, different is at 300 ℃, 0.15MPa, cis-butenedioic anhydride liquid air speed 0.5h
-1, under the hydrogen acid anhydride mol ratio condition of 200: 1, catalyst is evaluated.The cooling collection product of ice-water bath, adopts gas chromatographic analysis, and cis-butenedioic anhydride conversion ratio is 100%, and gamma-butyrolacton is selectively greater than 95%, and catalyst is used 2000 hours continuously, active not obviously reduction.
Although above the specific embodiment of the present invention has been given to describe in detail and explanation; but what should indicate is; we can carry out various equivalences to above-mentioned embodiment according to conception of the present invention and change and revise; when its function producing does not exceed spiritual that description contains yet, all should be within protection scope of the present invention.
Claims (10)
1. a catalyst for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation, is characterized in that described catalyst is by CuO, ZnO, Al
2o
3form with active carbon, the weight percent content of each component is: CuO10～40%, ZnO10～40%, Al
2o
310～40%, active carbon 1～25%.
2. the catalyst of preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation according to claim 1, is characterized in that the weight percent content of described each component is: CuO15～35%, ZnO15～35%, Al
2o
315～35%, active carbon 2～10%.
3. a preparation method for catalyst claimed in claim 1, adopts suspension coprecipitation, and active carbon is suspended in deionized water, adds the nitrate of Cu, Zn and Al, wherein Cu (NO
3)
23H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o and active carbon weight ratio are Cu (NO
3)
23H
2o: Zn (NO
3)
26H
2o: Al (NO
3)
39H
2o: active carbon=35～45: 35～45: 45～55: 1.5～12; At 60～80 ℃, stir 1～4h, then add precipitating reagent, control precipitation temperature at 60～80 ℃, controlling pH is 6～8, after precipitation process finishes, ageing 12～24h, then filter, wash, dry 8～12h at 80～130 ℃, roasting 3～4h at 300～400 ℃, compression molding, fragmentation.
4. method for preparing catalyst according to claim 3, is characterized in that described active carbon is 100～200 orders.
5. the preparation method of catalyst according to claim 3, is characterized in that described precipitating reagent is Na
2cO
3, NaHCO
3, NaOH, K
2cO
3, KHCO
3, KOH, (NH
4)
2cO
3, NH
4hCO
3, one or more in ammoniacal liquor.
6. the preparation method of catalyst according to claim 5, is characterized in that described precipitating reagent is Na
2cO
3.
7. the preparation method of catalyst according to claim 3, is characterized in that described catalyst breakage to 20～40 order granular size.
8. the preparation method of catalyst according to claim 3, is characterized in that described Cu (NO
3)
23H
2o: Zn (NO
3)
26H
2o: Al (NO
3)
39H
2o: active carbon=40: 40: 50: 1.5～12.
9. a catalyst hydrogenation cis-butenedioic anhydride claimed in claim 1 is prepared the application of gamma-butyrolacton, after comprising that cis-butenedioic anhydride steam and hydrogen mix, gaseous phase materials is by being equipped with the step of the fixed bed of catalyst, it is characterized in that described catalytic reaction condition is: 270～300 ℃ of reaction temperatures, reaction pressure 0.1～0.15MPa, cis-butenedioic anhydride liquid hourly space velocity (LHSV) 0.1～0.5h
-1, hydrogen and cis-butenedioic anhydride mol ratio 20: 1～200: 1.
10. catalyst hydrogenation cis-butenedioic anhydride according to claim 9 is prepared the application of gamma-butyrolacton, it is characterized in that, before described catalytic reaction, also comprise the activation step of catalyst, adopt the hydrogen of nitrogen dilution to activate catalyst, under 0.1～0.5MPa pressure, in 270～300 ℃, in fixed bed reactors, carry out in-situ reducing, until reactor outlet end dry-steam.
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| CN111097427A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride liquid-phase hydrogenation, preparation method and application thereof, and method for preparing gamma-butyrolactone |
| CN111097428A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride liquid-phase hydrogenation, preparation method and application thereof, and method for preparing gamma-butyrolactone |
| CN111097443A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation, preparation method and application of catalyst and method for preparing gamma-butyrolactone |
| CN111097444A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation, preparation method and application of catalyst and method for preparing gamma-butyrolactone |
| CN112138670A (en) * | 2020-10-15 | 2020-12-29 | 中国石油大学(华东) | Catalyst containing copper, zinc and aluminum, preparation method and application thereof |
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| CN1646514A (en) * | 2002-04-30 | 2005-07-27 | 巴斯福股份公司 | Method for producing gamma-butyrolactone |
| CN102247853A (en) * | 2011-05-23 | 2011-11-23 | 广州大学 | Catalyst for preparing gamma-butyrolactone through maleic anhydride normal-pressure gas-phase hydrogenation |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097427A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride liquid-phase hydrogenation, preparation method and application thereof, and method for preparing gamma-butyrolactone |
| CN111097428A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride liquid-phase hydrogenation, preparation method and application thereof, and method for preparing gamma-butyrolactone |
| CN111097443A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation, preparation method and application of catalyst and method for preparing gamma-butyrolactone |
| CN111097444A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation, preparation method and application of catalyst and method for preparing gamma-butyrolactone |
| CN112138670A (en) * | 2020-10-15 | 2020-12-29 | 中国石油大学(华东) | Catalyst containing copper, zinc and aluminum, preparation method and application thereof |
| CN112138670B (en) * | 2020-10-15 | 2023-12-08 | 中国石油大学(华东) | Copper-zinc-aluminum-containing catalyst and preparation method and application thereof |
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