CN101422732A - Catalyst for producing 1,4-butylediol and preparation method and use thereof - Google Patents
Catalyst for producing 1,4-butylediol and preparation method and use thereof Download PDFInfo
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- CN101422732A CN101422732A CNA200810243707XA CN200810243707A CN101422732A CN 101422732 A CN101422732 A CN 101422732A CN A200810243707X A CNA200810243707X A CN A200810243707XA CN 200810243707 A CN200810243707 A CN 200810243707A CN 101422732 A CN101422732 A CN 101422732A
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Abstract
The invention relates to a catalyst that is used for preparing 1,4-butanediol by diethyl succinate hydrogenation and a preparation method of the catalyst. In the total weight of the catalyst, cupric oxide accounts for 30 to 60 weight percent (Wt), zinc oxide accounts for 20 to 50 weight percent (Wt), and titanium oxide accounts for 5 to 20 weight percent (Wt). In the preparation, the dissoluble salts of copper, zinc and titanium are mixed according to the proportions thereof in the total weight of the catalyst and dissolved in deionized water, thus preparing a metallic ion mixture solution, under water-bath heated agitation, the metallic ion mixture solution and a precipitator are drop-added in current flow, the pH value of the solution is controlled between 7 and 8, the solution is agitated at constant temperature for 1 to 3 hours, temperature is raised to 70 to 80 DEG C for aging for 2 to 20 hours, precipitate is filtered, the precursor precipitate is rinsed by deionized water so as to remove impurity ions, and then the precipitate is dried at the temperature of 110 to 120 DEG C for 8 to 12 hours and baked in a muffle furnace at the temperature of 350 to 550 DEG C for 3 to 5 hours. The invention has the advantages that the provided catalyst has standardized pore structure, higher specific surface, higher activity, good selectivity, and the production and recycling without environmental pollution.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of diethyl succinate hydrogenation preparing 1 that is used for, the catalyst of 4-butanediol and preparation method and application.
Background technology
1, the 4-butanediol is called for short BDO, be a kind of broad-spectrum basic organic chemical industry and fine chemical material, mainly contain 4 product chains: (1) produces polybutylene terephthalate (being called for short PBT), the PBT resin is a kind of novel thermoplastic polyesters engineering plastics, can be used for electronics, electrical equipment, automobile and other industries; (2) produce gamma-butyrolacton (being called for short GBL), gamma-butyrolacton has high reactivity, is mainly used in to produce vinyl pyrrolidone, PVP, N-methyl pyrrolidone etc.; (3) produce oxolane (being called for short THF), oxolane is mainly as solvent and medicine intermediate, and the polytetramethylene ether diol that oxolane is produced through ring-opening polymerisation is a base stock of producing the Lycra fiber; (4) produce PAUR (being called for short PU).Because the increasing rapidly of BDO downstream product demands such as PBT thermoplastic engineering plastic, polytetramethylene glycol ether, increasing by a relatively large margin also appearred in the demand of BDO thereupon in recent years, and China is annual to need a large amount of imports to satisfy the needs that downstream industry is produced.
Industrialized at present 1, the 4-butanediol is produced route and mainly contained 5 kinds: (1) is the Reppe method of raw material with formaldehyde and acetylene; (2) with the propylene be the synthesis technique of raw material; (3) with the butadiene be the synthesis technique of raw material; (4) with the cis-butenedioic anhydride be the hydrogenation technique of raw material; (5) the gas phase hydrogenation technology of maleic anhydride.Wherein most widely used is Reppe method technology, but the gas phase hydrogenation technology of maleate more and more comes into one's own.
EP0143634 discloses a kind of employing diethyl maleate and/or diethyl succinate gas phase hydrogenation preparation 1, and 4-butanediol, and the method for coproduction GBL and THF, used catalyst are the catalyst that contains Cu-Cr.It is raw material gas phase hydrogenation preparation 1 with maleic dialkyl and/or succinic acid dialkyl ester that CN1116616A discloses a kind of, the method for 4-butanediol, and the catalyst general formula is Cu
aZnCr
bM
cO
x(M is a kind of element that is selected from the IVB family, particularly Zr element).CN1137944A CuCr
aMn
bBa
cM
dO
x(M=Al or Ti), CN1182639A CuCr
aZn
bTi
cO
xHydrogenation maleic anhydride and/or its ester system 1, the 4-butanediol.Above catalyst all adopts chromium-containing oxide type catalyst, though they have advantages of high catalytic activity and good selectivity, the manufacturing of this class catalyst and recovery all can have serious pollution to environment.
Summary of the invention
The invention provides a kind of diethyl succinate gas phase hydrogenation system 1 that is used for, the catalyst of 4-butanediol and preparation method and application.
The present invention is used for diethyl succinate gas phase hydrogenation system 1, and the catalyst of 4-butanediol is by the active component cupric oxide, and auxiliary agent zinc oxide, titanium oxide three components are formed,
Cupric oxide accounts for 30～60% (Wt) in total catalyst weight, and zinc oxide accounts for 20～50% (Wt), and titanium oxide accounts for 5～20% (Wt).
Catalyst of the present invention makes with coprecipitation, the solubility salt of copper, zinc and titanium such as nitrate or chloride are accounted for 30～60% (Wt) by its cupric oxide in total catalyst weight, zinc oxide accounts for 20～50% (Wt), after titanium oxide accounts for the ratio mixing of 5～20% (Wt), use deionized water dissolving, be made into metallic ion mixed liquor, the metal ion total concentration is 0.5～1.5M, precipitating reagent is selected sodium carbonate, ammoniacal liquor or NaOH for use, precipitant solution concentration is 0.5～1.5M, and concrete concentration is decided according to metal concentration.Under stirring fast, these two parts of solution and drip are added, the heating of water-bath simultaneously, the control bath temperature is at 50～70 ℃, and the control pH value of solution is 7～8.Drip and finish, constant temperature stirred 1～3 hour, was warming up to 70～80 ℃ and wore out 2～20 hours, filtering-depositing, spend deionised water presoma precipitation and remove foreign ion, 110～120 ℃ dry 8～12 hours down, 350～550 ℃ of following roastings 3～5 hours in Muffle furnace then.Can obtain catalyst of the present invention after the compressing tablet granulation.
After the soluble-salt of copper, zinc and titanium mixed in its ratio in total catalyst weight, use deionized water dissolving, be made into metallic ion mixed liquor, add under the thermal agitation in water-bath metallic ion mixed liquor and precipitating reagent and drip are added, the control pH value of solution is 7～8, after dropwising, heated up aging 2～20 hours, filter then, washing, collecting precipitation, 110～120 ℃ dry 2～12 hours down, 350～550 ℃ of following roastings 3～10 hours; Wherein the soluble-salt of copper, zinc and titanium is nitrate or chloride; Precipitating reagent is selected from ammoniacal liquor, NaOH, sodium carbonate or sodium acid carbonate; Precipitant solution concentration is 0.5～1.5M, and the temperature of water-bath heating is controlled at 50～80 ℃, and aging temperature is controlled at 70～100 ℃
The used catalyst of the present invention need reduce before use, and reducing agent can adopt the mixed gas of reducibility gas such as hydrogen, carbon monoxide or they and nitrogen, and reduction is carried out under 0.1～2.0MPa, 160～300 ℃.
Activity of such catalysts provided by the invention can be tested with the following method:
Catalyst activity is investigated in catalyst powder granulation to 20 after the roasting～40 orders in micro fixed-bed reactor, with the hydrogen reducing activation of dilution.The raw material diethyl succinate is dissolved in ethanol (v/v=1/4) as reactant liquor, squeezes in the reaction tube through micropump, and pressurization heats up and reacts then.Reaction pressure is 4～6MPa, and reaction temperature is 180～240 ℃.The hydrogen ester mol ratio is 50～250:1, and the liquid hourly space velocity (LHSV) of ester is 0.05～2.0h
-1Product after condensation with its composition of gas chromatographic analysis.
In the catalyst that advantage of the present invention provides, active ingredient copper is dispersed in zinc oxide and the titanium oxide, have regular pore structure and higher specific surface area, the selectivity that activity of such catalysts is higher and good, and the manufacturing of catalyst and reclaim can not pollute environment.
The specific embodiment
Embodiment 1:
182.2g copper nitrate (Cu (NO
3)
23H2O), 73.1g zinc nitrate (Zn (NO
3)
26H
2O) and 74.1g Titanium Nitrate (Ti (NO
3)
4) be dissolved in the 1000ml deionized water, make solution A.With 53gNa
2CO
3Be dissolved in the 1000ml deionized water, make solution B.Two kinds of solution of A, B are added in water-bath add simultaneously under the thermal agitation in the beaker, bath temperature is controlled at 60 ℃, control A, two kinds of solution of B drip speed, make the pH of solution remain at 7～8.Continuation was stirred 2 hours after titration finished, and was warming up to 80 ℃ and wore out 2 hours, and suction filtration washs then, and drying is 8 hours under 110 ℃, and 450 ℃ of roastings promptly got catalyst A in 5 hours, under 0.1MPa, and 160 ℃ of conditions hydrogen reducing, stand-by.
Embodiment 2:
182.2g copper nitrate (Cu (NO
3)
23H
2O), 109.7g zinc nitrate (Zn (NO
3) 26H
2O) and 37.0g Titanium Nitrate (Ti (NO
3)
4) be dissolved in the 1000ml deionized water, make solution A.With 106gNa
2CO
3Be dissolved in the 1000ml deionized water, make solution B.Two kinds of solution of A, B are added in water-bath add simultaneously under the thermal agitation in the beaker, bath temperature is controlled at 60 ℃, control A, two kinds of solution of B drip speed, make the pH of solution remain at 7～8.Continuation was stirred 2 hours after titration finished, and was warming up to 80 ℃ and wore out 2 hours, and suction filtration washs then, and drying is 8 hours under 110 ℃, and 450 ℃ of roastings promptly got catalyst B in 5 hours, and under 0.5MPa, 200 ℃ of conditions are reduced with carbon monoxide, and are stand-by.
Embodiment 3:
169.0g copper chloride (CuCl
2), 134.0g zinc chloride (ZnCl
2) and 47.5g titanium tetrachloride (TiCl
4) be dissolved in the 1000ml deionized water, make solution A.60gNaOH is dissolved in the 1000ml deionized water, makes solution B.Two kinds of solution of A, B are added in water-bath add simultaneously under the thermal agitation in the beaker, bath temperature is controlled at 60 ℃, control A, two kinds of solution of B drip speed, make the pH of solution remain at 7～8.Continuation was stirred 2 hours after titration finished, and was warming up to 80 ℃ and wore out 2 hours, and suction filtration washs then, and drying is 8 hours under 110 ℃, and 450 ℃ of roastings promptly got catalyst C in 5 hours, and under 1.0MPa, 200 ℃ of conditions are reduced with nitrogen, and are stand-by.
Embodiment 4:
135.2g copper chloride (CuCl
2), 134.0g zinc chloride (ZnCl
2) and 95.0g titanium tetrachloride (TiCl
4) be dissolved in the 1000ml deionized water, make solution A.The 35g ammonia solvent in the 1000ml deionized water, is made solution B.Two kinds of solution of A, B are added in water-bath add simultaneously under the thermal agitation in the beaker, bath temperature is controlled at 60 ℃, control A, two kinds of solution of B drip speed, make the pH of solution remain at 7～8.Continuation was stirred 2 hours after titration finished, and was warming up to 80 ℃ and wore out 2 hours, and suction filtration washs then, and drying is 8 hours under 110 ℃, and 450 ℃ of roastings promptly got catalyst D in 5 hours, and under 1.5MPa, 250 ℃ of conditions are reduced with carbon monoxide, and are stand-by.
Embodiment 5:
Adopt the catalyst A of embodiment 1 preparation to carry out diethyl succinate hydrogenation system 1, the reaction experiment of 4-butanediol.The loadings of catalyst is 5g, experimentizes under different technology conditions, and the result is as shown in the table.
| Reaction temperature (℃) | Reaction pressure (MPa) | Liquid hourly space velocity (LHSV) (h -1) | Hydrogen ester mol ratio (mol/mol) | Ester conversion rate (%) | Alcohol selectivity (%) |
| 180 | 4.0 | 0.2 | 150 | 93.4 | 78.5 |
| 180 | 4.0 | 0.2 | 200 | 96.8 | 82.1 |
| 210 | 4.0 | 0.2 | 100 | 95.0 | 75.9 |
| 210 | 4.0 | 0.2 | 200 | 98.3 | 81.5 |
| 240 | 4.0 | 0.2 | 200 | 98.8 | 79.2 |
| 240 | 5.9 | 0.2 | 200 | 98.9 | 80.6 |
Embodiment 6:
Adopt the catalyst B of embodiment 2 preparations to carry out diethyl succinate hydrogenation system 1, the reaction experiment of 4-butanediol.The loadings of catalyst is 5g, experimentizes under different technology conditions, and the result is as shown in the table.
| Reaction temperature (℃) | Reaction pressure (MPa) | Liquid hourly space velocity (LHSV) (h -1) | Hydrogen ester mol ratio (mol/mol) | Ester conversion rate (%) | Alcohol selectivity (%) |
| 180 | 4.0 | 0.2 | 150 | 94.8 | 80.8 |
| 180 | 4.0 | 0.2 | 200 | 97.2 | 87.2 |
| 210 | 4.0 | 0.2 | 100 | 95.9 | 75.9 |
| 210 | 4.0 | 0.2 | 200 | 98.9 | 84.5 |
| 240 | 4.0 | 0.2 | 200 | 99.2 | 81.0 |
| 240 | 5.9 | 0.2 | 200 | 99.5 | 85.7 |
Embodiment 7:
Adopt the catalyst C of embodiment 3 preparations to carry out diethyl succinate hydrogenation system 1, the reaction experiment of 4-butanediol.The loadings of catalyst is 5g, experimentizes under different technology conditions, and the result is as shown in the table.
| Reaction temperature (℃) | Reaction pressure (MPa) | Liquid hourly space velocity (LHSV) (h -1) | Hydrogen ester mol ratio (mol/mol) | Ester conversion rate (%) | Alcohol selectivity (%) |
| 180 | 4.0 | 0.2 | 150 | 96.2 | 78.8 |
| 180 | 4.0 | 0.2 | 200 | 97.8 | 88.0 |
| 210 | 4.0 | 0.2 | 100 | 95.5 | 75.3 |
| 210 | 4.0 | 0.2 | 200 | 98.3 | 84.7 |
| 240 | 4.0 | 0.2 | 200 | 99.1 | 80.2 |
| 240 | 5.9 | 0.2 | 200 | 99.6 | 82.6 |
Embodiment 8:
Adopt the catalyst D of embodiment 4 preparations to carry out diethyl succinate hydrogenation system 1, the reaction experiment of 4-butanediol.The loadings of catalyst is 5g, experimentizes under different technology conditions, and the result is as shown in the table.
| Reaction temperature (℃) | Reaction pressure (MPa) | Liquid hourly space velocity (LHSV) (h -1) | Hydrogen ester mol ratio (mol/mol) | Ester conversion rate (%) | Alcohol selectivity (%) |
| 180 | 4.0 | 0.2 | 150 | 90.7 | 73.5 |
| 180 | 4.0 | 0.2 | 200 | 94.3 | 80.6 |
| 210 | 4.0 | 0.2 | 100 | 91.5 | 72.7 |
| 210 | 4.0 | 0.2 | 200 | 95.3 | 78.5 |
| 240 | 4.0 | 0.2 | 200 | 97.8 | 75.2 |
| 240 | 5.9 | 0.2 | 200 | 98.5 | 77.3 |
Claims (6)
1. one kind is used for diethyl succinate hydrogenation preparing 1, the catalyst of 4-butanediol, it is characterized in that: catalyst is made up of cupric oxide, zinc oxide and three kinds of components of titanium oxide, in total catalyst weight, cupric oxide accounts for 30～60%W), zinc oxide accounts for 20～50%Wt, and titanium oxide accounts for 5～20%Wt.
2. described diethyl succinate hydrogenation preparing 1 that is used for of claim 1, the Preparation of catalysts method of 4-butanediol, it is characterized in that: with copper, after the soluble-salt of zinc and titanium mixes in its ratio in total catalyst weight, use deionized water dissolving, be made into metallic ion mixed liquor, add under the thermal agitation in water-bath metallic ion mixed liquor and precipitating reagent and drip are added, the control pH value of solution is 7～8, drip and finish, constant temperature stirred 1～3 hour, being warming up to 70～80 ℃ wore out 2～20 hours, filtering-depositing, spend deionised water presoma precipitation and remove foreign ion, 110～120 ℃ dry 8～12 hours down, 350～550 ℃ of following roastings 3～5 hours in Muffle furnace then; Wherein the soluble-salt of copper, zinc and titanium is nitrate or chloride; Precipitating reagent is selected from ammoniacal liquor, NaOH, sodium carbonate or sodium acid carbonate; Precipitant solution concentration is 0.5～1.5M, and the temperature of water-bath heating is controlled at 50～80 ℃, and aging temperature is controlled at 70～100 ℃.
3. according to the described preparation method of claim 2, it is characterized in that: the temperature of water-bath heating is controlled at 60～70 ℃.
4. according to the described preparation method of claim 2, it is characterized in that: aging temperature is controlled at 75～85 ℃.
5. the described catalyst of claim 1 is used for diethyl succinate hydrogenation preparing 1, the application of 4-butanediol, it is characterized in that: catalyst need reduce before use, reducing agent adopts the mixed gas of reducibility gas hydrogen, carbon monoxide or they and nitrogen, reduces under 0.1～2.0MPa, 160～300 ℃.
6. catalyst according to claim 6 is used for diethyl succinate hydrogenation preparing 1, and the application of 4-butanediol is characterized in that the temperature of using is 160～260 ℃, and reaction pressure is 3.0～8.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810243707XA CN101422732A (en) | 2008-12-12 | 2008-12-12 | Catalyst for producing 1,4-butylediol and preparation method and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810243707XA CN101422732A (en) | 2008-12-12 | 2008-12-12 | Catalyst for producing 1,4-butylediol and preparation method and use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551154A (en) * | 2013-10-31 | 2014-02-05 | 西北化工研究院 | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst |
| US9168509B2 (en) | 2011-11-09 | 2015-10-27 | China Petroleum & Chemical Corp. | Hydrogenation catalysts and the preparation processes thereof |
| CN108607562A (en) * | 2018-05-03 | 2018-10-02 | 中溶科技股份有限公司 | Catalyst and preparation method and application for hexanedioic acid dialkyl ester hexylene glycol |
-
2008
- 2008-12-12 CN CNA200810243707XA patent/CN101422732A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9168509B2 (en) | 2011-11-09 | 2015-10-27 | China Petroleum & Chemical Corp. | Hydrogenation catalysts and the preparation processes thereof |
| CN103551154A (en) * | 2013-10-31 | 2014-02-05 | 西北化工研究院 | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst |
| CN103551154B (en) * | 2013-10-31 | 2015-02-18 | 西北化工研究院 | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst |
| CN108607562A (en) * | 2018-05-03 | 2018-10-02 | 中溶科技股份有限公司 | Catalyst and preparation method and application for hexanedioic acid dialkyl ester hexylene glycol |
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Application publication date: 20090506 |