CN103611546A - Bimetal catalyst for synthesizing butanedioic-acid dialkyl ester and preparation method thereof - Google Patents
Bimetal catalyst for synthesizing butanedioic-acid dialkyl ester and preparation method thereof Download PDFInfo
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Abstract
The invention relates to bimetal catalyst for synthesizing butanedioic-acid dialkyl ester and a preparation method thereof. The active components of the catalyst are ruthenium, iron, and nickel or copper, and a carrier is aluminum oxide, silicon dioxide and titanium dioxide. The preparation method is characterized in that on the basis of CN102600836a, the high-activity catalyst is prepared by introducing a second metal component and adopting an adsorption-precipitation method, the high-activity catalyst can be used for catalyzing maleic-acid dialkyl ester to synthesize butanedioic-acid dialkyl ester through hydrogenation under the conditions of low temperature and low pressure, and the selectivity and the conversion rate can reach up to over 99 percent; and the activity of the bimetal catalyst is doubled under the condition of the identical heavy-metal content, the consumption of the precious metal can be reduced while the identical catalytic activity is maintained, the cost of the catalyst is reduced, and the benefit can be maximized. The catalyst has the advantages of low cost, good stability, high activity, high selectivity and the like.
Description
Technical field
The present invention relates to a kind of synthesizing succinic acid dialkyl catalyst and preparation method.
Technical background
Succinic acid dialkyl ester is the important synthetic perfume of a class, food additives, and environment protection type high-boiling-point solvent is also a kind of important chemical intermediate simultaneously, is widely used in food, spices, medicine.The industries such as coating, rubber, plastics.Especially along with people's environmental consciousness strengthens, the chemical products of environmental protection enjoy favor, the environmental protection coating material that the succinic acid dialkyl of take is solvent and the high performance pigments (as pyrrolo-pyrrole-dione) of preparing as intermediate will have huge market prospects, and this will drive the market demand of succinic acid dialkyl ester.
The main method of industrial synthesizing succinic acid dialkyl is to adopt the concentrated sulfuric acid to make catalyst to be reacted and obtain with alcohol by succinic acid.But sulfuric acid has highly acid and severe corrosive, both increased equipment investment cost, cause again this technique side reaction many, product yield is low, shade deviation, simultaneously contaminated environment.The focus of people's research in recent years mainly concentrates on and adopts solid acid to replace the synthetic related esters series products of sulphur acid as catalyst.
Patent CN101745396A, CN101747189A have announced technique and the catalyst of dialkyl maleate catalytic hydrogenation synthesizing succinic acid dialkyl, and catalyst used is copper zinc catalyst.The problem existing is mainly that active component content is high, and the impact of being heated is poor, and reaction pressure is high, and copper catalyst, as the most frequently used carbonyl hydrogen catalyst, is easy to generate the accessory substances such as BDO, gamma-butyrolacton, oxolane simultaneously, has increased separation costs.
Patent CN101979139A discloses a kind of nickel catalyst carried preparation method and application by dimethyl maleate hydrogenation synthesis of dimethyl succinate, for keeping higher catalytic activity, reaction temperature need be carried out under higher temperature (200 ℃, 0.5MPa) or higher pressure (50 ℃, 5MPa).
US5872276A discloses a kind of method of dialkyl maleate catalytic hydrogenation synthesizing succinic acid dialkyl, adopts insulation fix bed reactor, and catalyst used is Ni/Zr/Al.The method reaction pressure is up to 30MPa.
CN102600836A discloses a kind of method for preparing catalyst and application by alkyl maleate hydrogenation synthesizing succinic acid dialkyl, and catalyst used is load ruthenium catalyst, has realized 50～90 ℃, and pressure is lower than the highly effective hydrogenation under 10atm condition.It is active component that this catalyst is used 0.5～15% noble ruthenium, and catalyst preparation cost is relatively high, and it is vital therefore how further reducing bullion content.
Summary of the invention
The object of the present invention is to provide bimetallic catalyst of a kind of synthesizing succinic acid dialkyl and preparation method thereof, this catalyst activity component is ruthenium and iron, nickel or copper, carrier is aluminium oxide, silica, titanium dioxide, the method is on CN102600836A basis, by introducing the second metal component, adopt absorption-deposition method to prepare high activated catalyst, can be at catalysis alkyl maleate hydrogenation synthesizing succinic acid dialkyl under low-temp low-pressure, selective and conversion ratio all reaches more than 99.0%; Under identical bullion content condition, the active twice that improves of bimetallic catalyst, while keeping equal catalytic activity, can reduce the use amount of noble metal, has reduced catalyst cost, reaches maximizing the benefits.It is low that this catalyst has cost, good stability, activity and selectivity advantages of higher.
The bimetallic catalyst of a kind of synthesizing succinic acid dialkyl of the present invention, this catalyst activity component is ruthenium and iron, nickel or copper, carrier is aluminium oxide, silica, one or both in titanium dioxide, the content of ruthenium is 0.1-5.0% by weight percentage, the content of iron, nickel or copper is 0.5-20%, and the content of carrier is 99.4-75%.
The preparation method of the bimetallic catalyst of described succinic acid dialkyl ester, is adsorption precipitation method, and concrete operations follow these steps to carry out:
A, ruthenium trichloride and iron chloride, nickel nitrate or copper nitrate are dissolved in to deionized water, are fully uniformly mixed, then adding carrier is aluminium oxide, silica, and titanium dioxide continues to stir 1-24h;
B, add alkaline solution to regulate pH=9-10 step a solution, continue to stir 0.5-24h, standing over night, suction filtration, then with deionized water washing to without chlorion, dry, then roasting reduction, obtains bimetallic catalyst.
Step b neutral and alkali solution is ammoniacal liquor, the potassium hydroxide that urea liquid or concentration are 0.1-10mol/L, NaOH, potash or sodium carbonate liquor.
In step b, calcination atmosphere is argon gas or air, and sintering temperature is 100-700 ℃, and reducing agent is gaseous mixture, sodium borohydride or the ethylene glycol of hydrogen, hydrogen and argon gas, and reduction temperature is 20-700 ℃.
The bimetallic catalyst of synthesizing succinic acid dialkyl of the present invention is compared with existing catalyst, has feature to be:
This catalyst has reduced the use amount of noble ruthenium, has reduced catalyst cost, and has good heat endurance under low-temp low-pressure, high activity and selective.The catalyst of preparing by the method for the invention can be at temperature 30-90 ℃, catalysis alkyl maleate hydrogenation synthesizing succinic acid dialkyl under pressure 2-15atm, and selective and conversion ratio all reaches more than 99.0%.
The specific embodiment
Embodiment 1(contrast)
120mg ruthenium trichloride is dissolved in to 50mL deionized water, is fully uniformly mixed, then add carrier 10g aluminium oxide, continue to stir 4h;
Add again 1mol/L sodium hydroxide solution to regulate pH=9～10, continue to stir 4h, standing over night; Suction filtration, deionized water washing is to neutral simultaneously without chlorion, at room temperature after dry, roasting, reductase 12 h in 400 ℃ of hydrogen atmospheres of temperature, hydrogen gas space velocity is 400h
-1, obtain catalyst 1.
Embodiment 2(contrast)
240mg ruthenium trichloride is dissolved in to 50mL deionized water, is fully uniformly mixed, then add carrier 10g aluminium oxide, continue to stir 4h;
Add again 1mol/L sodium hydroxide solution to regulate pH=9～10, continue to stir 4h, standing over night; Suction filtration, deionized water washing is to neutral simultaneously without chlorion; At room temperature dry, reductase 12 h in 400 ℃ of hydrogen atmospheres, hydrogen gas space velocity is 600h
-1, obtain catalyst 2.
Embodiment 3(the present invention)
120mg ruthenium trichloride and 500mg nickel nitrate are dissolved in 50mL deionized water, are fully uniformly mixed, then add carrier 10g aluminium oxide, continue to stir 4h;
Adding concentration is that 1mol/L sodium hydroxide solution regulates pH=9 again, continues to stir 4h, standing over night; Suction filtration, then with deionized water washing to without chlorion, at room temperature dry, roasting reduction then, calcination atmosphere is air, sintering temperature is 100 ℃, reductase 12 h in hydrogen atmosphere, 400 ℃ of reduction temperatures, hydrogen gas space velocity is 400h
-1, obtain bimetallic catalyst 3.
Embodiment 4(the present invention)
120mg ruthenium trichloride and 1.2g copper nitrate are dissolved in 50mL deionized water, are fully uniformly mixed, then add carrier 10g silica, continue to stir 4h;
Adding concentration is that 0.1mol/L potassium hydroxide solution regulates pH=10 again, continue to stir 4h, standing over night, suction filtration, by deionized water, wash extremely without chlorion again, at room temperature dry, roasting reduction then, calcination atmosphere is argon gas, sintering temperature is 200 ℃, at reducing agent, be the mist reductase 12 h of hydrogen and argon gas, reduction temperature is 200 ℃, and the mist air speed of hydrogen and argon gas is 600h
-1, obtain bimetallic catalyst 4.
Embodiment 5(the present invention)
120mg ruthenium trichloride and 600mg iron chloride are dissolved in 50mL deionized water, are fully uniformly mixed, then add carrier 10g titanium dioxide, continue to stir 4h;
Adding concentration is that 2mol/L sodium carbonate liquor regulates pH=10 again, continue to stir 4h, standing over night, suction filtration, by deionized water, wash extremely without chlorion again, at room temperature dry, roasting reduction then, calcination atmosphere is argon gas, sintering temperature is 700 ℃, with sodium borohydride reduction activation, reduction temperature is 20 ℃, obtains bimetallic catalyst 5.
Embodiment 6(the present invention)
Ruthenium trichloride 120mg and nickel nitrate 600mg are dissolved in 50mL deionized water, are fully uniformly mixed, then add carrier 10g aluminium oxide, continue to keep 1h;
Add again mass fraction 25% ammoniacal liquor to regulate pH=9, continue to stir 0.5h, standing over night, standing over night, suction filtration, then wash to without chlorion by deionized water, at room temperature dry, then roasting reduction, calcination atmosphere is air, and sintering temperature is 200 ℃, and reducing agent is ethylene glycol, reduction temperature is 80 ℃, obtains bimetallic catalyst 6.
Embodiment 7(the present invention)
Ruthenium trichloride 120mg and nickel nitrate 600mg are dissolved in 50mL deionized water, are fully uniformly mixed, then add carrier 10g silica, continue to keep 5h;
Add again mass fraction 10% urea liquid to regulate pH=10, continue to stir 5h, standing over night, suction filtration, then wash to without chlorion by deionized water, at room temperature dry, hydrogen atmosphere reduction, reduction temperature is 700 ℃, hydrogen gas space velocity is 400h
-1, obtain bimetallic catalyst 7.
Embodiment 8(the present invention)
Ruthenium trichloride 120mg and nickel nitrate 600mg are dissolved in 50mL deionized water, are fully uniformly mixed, then adding carrier is titanium dioxide 10g, continues to stir 10h;
Adding concentration is the potassium alkaline solution adjusting pH=10 of 5mol/L again, continue to stir 10h, standing over night, suction filtration, by deionized water, wash extremely without chlorion again, at room temperature dry, roasting reduction then, calcination atmosphere is air, sintering temperature is 400 ℃, reducing agent is ethylene glycol, and reduction temperature is 100 ℃, obtains bimetallic catalyst 8.
Embodiment 9(the present invention)
Ruthenium trichloride 60mg and nickel nitrate 250mg are dissolved in 50mL deionized water, are fully uniformly mixed, then adding carrier is the mixture 10g of silica and aluminium oxide, continues to stir 24h;
Adding concentration is the potassium alkaline solution adjusting pH=9 of 10mol/L again, continues to stir 24h, standing over night, suction filtration, by deionized water, wash to without chlorion again, at room temperature dry, reduction activation, reducing agent is ethylene glycol, and reduction temperature is 100 ℃, obtains bimetallic catalyst 9.
Embodiment 10
By any one catalyst of embodiment 3-9 gained, for the synthesis of succinic acid dialkyl ester, concrete steps are:
By catalyst 200mg, dimethyl maleate 10g, methyl alcohol 90mL adds in 200mL autoclave successively, airtight, nitrogen blowing three times, then hydrogen purge once, is warming up to 65 ℃, regulate hydrogen reaction pressure 8-10atm, open magnetic agitation, start reaction, to consuming hydrogen gas rate while being zero, reaction finishes, and reacted mixture adopts gas chromatographic analysis;
Table 1 reaction condition and catalyst activity evaluation result:
The presentation of results that embodiment 3-10 catalyst activity is evaluated, by introducing the second metal component, adopt the standby bimetallic catalyst of absorption-deposition legal system, can be at catalysis alkyl maleate hydrogenation synthesizing succinic acid dialkyl under low-temp low-pressure, selective and conversion ratio all reaches more than 99.0%, under identical bullion content condition, the active twice that improves of bimetallic catalyst; When keeping equal catalytic activity, can reduce the use amount of noble metal, reduced catalyst cost.
Claims (4)
1. the bimetallic catalyst of a synthesizing succinic acid dialkyl, it is characterized in that this catalyst is by active component ruthenium and iron, nickel or copper, carrier is aluminium oxide, silica, one or both in titanium dioxide, the content of ruthenium is 0.1-5.0% by weight percentage, the content of iron, nickel or copper is 0.5-20%, and the content of carrier is 99.4-75%.
2. the preparation method of the bimetallic catalyst of succinic acid dialkyl ester according to claim 1, is characterized in that, for adsorption precipitation method, concrete operations follow these steps to carry out:
A, ruthenium trichloride and iron chloride, nickel nitrate or copper nitrate are dissolved in to deionized water, are fully uniformly mixed, then adding carrier is aluminium oxide, silica, and titanium dioxide continues to stir 1-24 h;
B, add alkaline solution to regulate pH=9-10 step a solution, continue to stir 0.5-24 h, standing over night, suction filtration, then with deionized water washing to without chlorion, dry, then roasting reduction, obtains bimetallic catalyst.
3. method according to claim 2, is characterized in that step b neutral and alkali solution is ammoniacal liquor, and urea liquid or concentration are potassium hydroxide, NaOH, potash or the sodium carbonate liquor of 0.1-10 mol/L.
4. method according to claim 2, is characterized in that in step b, calcination atmosphere is argon gas or air, and sintering temperature is 100-700 ℃, and reducing agent is gaseous mixture, sodium borohydride or the ethylene glycol of hydrogen, hydrogen and argon gas, and reduction temperature is 20-700 ℃.
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Cited By (1)
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| CN105435813A (en) * | 2015-11-05 | 2016-03-30 | 中国科学院青岛生物能源与过程研究所 | Bimetallic catalyst for preparing methyl butyrolactone through heterogeneous catalytic hydrogenation and preparation method thereof |
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Patent Citations (4)
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| US20090111948A1 (en) * | 2007-10-25 | 2009-04-30 | Thomas Eugene Dueber | Compositions comprising polyimide and hydrophobic epoxy and phenolic resins, and methods relating thereto |
| CN102070448A (en) * | 2011-02-22 | 2011-05-25 | 湖南长岭石化科技开发有限公司 | Method for preparing dimethyl succinate |
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| CN105435813A (en) * | 2015-11-05 | 2016-03-30 | 中国科学院青岛生物能源与过程研究所 | Bimetallic catalyst for preparing methyl butyrolactone through heterogeneous catalytic hydrogenation and preparation method thereof |
| CN105435813B (en) * | 2015-11-05 | 2018-05-29 | 中国科学院青岛生物能源与过程研究所 | For heterogeneous catalysis Hydrogenation for bimetallic catalyst of methylbutyrolactone and preparation method thereof |
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