CN103611546B - Bimetallic catalyst of a kind of synthesizing succinic acid dialkyl and preparation method thereof - Google Patents
Bimetallic catalyst of a kind of synthesizing succinic acid dialkyl and preparation method thereof Download PDFInfo
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- CN103611546B CN103611546B CN201310676463.5A CN201310676463A CN103611546B CN 103611546 B CN103611546 B CN 103611546B CN 201310676463 A CN201310676463 A CN 201310676463A CN 103611546 B CN103611546 B CN 103611546B
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Abstract
The present invention relates to 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, adopts absorption-deposition method to prepare high activated catalyst, can 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, bimetallic catalyst activity improves twice, when namely keeping equal catalytic activity, can reduce the use amount of noble metal, reduce catalyst cost, reach maximizing the benefits.It is low that this catalyst has cost, good stability, activity and selectivity advantages of higher.
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, take succinic acid dialkyl as the environmental protection coating material of solvent and will have huge market prospects for the high performance pigments (as pyrrolo-pyrrole-dione) of Intermediate Preparation, this will drive the market demand of succinic acid dialkyl ester.
The main method of industrial synthesizing succinic acid dialkyl adopts the concentrated sulfuric acid to make catalyst to be obtained by reacting by succinic acid and alcohol.But sulfuric acid has highly acid and severe corrosive, both added 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 sulphur acid as catalyst synthesis related esters series products.
Patent CN101745396A, CN101747189A disclose technique and the catalyst of dialkyl maleate catalytic hydrogenation synthesizing succinic acid dialkyl, and catalyst used is copper zinc catalyst.Problems existing mainly active component content is high, and heat-shock is poor, and reaction pressure is high, and copper catalyst is as the most frequently used carbonyl hydrogen catalyst simultaneously, and be easy to generate BDO, the accessory substance such as gamma-butyrolacton, oxolane, adds separation costs.
Patent CN101979139A discloses a kind of nickel catalyst carried preparation method by dimethyl maleate hydrogenation synthesis dimethyl succinate and application, for keeping higher catalytic activity, reaction temperature need be carried out at higher temperature (200 DEG C, 0.5MPa) or higher pressure (50 DEG C, 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 by alkyl maleate hydrogenation synthesizing succinic acid dialkyl and application, and catalyst used is load ruthenium catalyst, achieves 50 ~ 90 DEG C, and pressure is lower than the highly effective hydrogenation under 10atm condition.This catalyst uses 0.5 ~ 15% noble ruthenium to be active component, and catalyst preparing cost is relatively high, and it is vital for therefore how reducing bullion content further.
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, absorption-deposition method is adopted to prepare high activated catalyst, can 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, bimetallic catalyst activity improves twice, when namely keeping equal catalytic activity, can reduce the use amount of noble metal, reduce catalyst cost, reach 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, be 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 deionized water, be fully uniformly mixed, then adding carrier is aluminium oxide, silica, titanium dioxide, continues to stir 1-24h;
B, step a solution added alkaline solution and regulate pH=9-10, Keep agitation 0.5-24h, hold over night, suction filtration, then spend deionized water to without chlorion, drying, then roasting reduction, obtains bimetallic catalyst.
Step b neutral and alkali solution is ammoniacal liquor, and urea liquid or concentration are the potassium hydroxide of 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 DEG C, and reducing agent is the gaseous mixture of hydrogen, hydrogen and argon gas, sodium borohydride or ethylene glycol, and reduction temperature is 20-700 DEG C.
The bimetallic catalyst of synthesizing succinic acid dialkyl of the present invention is compared with existing catalyst, and having feature is:
This catalyst decreases the use amount of noble ruthenium, reduces catalyst cost, and has good heat endurance under low-temp low-pressure, high activity and selective.The catalyst prepared by the method for the invention can at temperature 30-90 DEG C, catalysis alkyl maleate hydrogenation synthesizing succinic acid dialkyl under pressure 2-15atm, and selective and conversion ratio all reaches more than 99.0%.
Detailed description of the invention
Embodiment 1(contrasts)
120mg ruthenium trichloride is dissolved in 50mL deionized water, is fully uniformly mixed, then add carrier 10g aluminium oxide, continue to stir 4h;
Add 1mol/L sodium hydroxide solution again and regulate pH=9 ~ 10, Keep agitation 4h, hold over night; Suction filtration, deionized water washing is to neutral simultaneously without chlorion, and at room temperature after drying, roasting, reductase 12 h in temperature 400 DEG C of hydrogen atmospheres, hydrogen gas space velocity is 400h
-1, obtain catalyst 1.
Embodiment 2(contrasts)
240mg ruthenium trichloride is dissolved in 50mL deionized water, is fully uniformly mixed, then add carrier 10g aluminium oxide, continue to stir 4h;
Add 1mol/L sodium hydroxide solution again and regulate pH=9 ~ 10, Keep agitation 4h, hold over night; Suction filtration, deionized water washing is to neutral simultaneously without chlorion; At room temperature dry, reductase 12 h in 400 DEG C 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 again that 1mol/L sodium hydroxide solution regulates pH=9, Keep agitation 4h, hold over night; Suction filtration, then spend deionized water extremely without chlorion, at room temperature dry, then roasting reduction, calcination atmosphere is air, and sintering temperature is 100 DEG C, reductase 12 h in hydrogen atmosphere, reduction temperature 400 DEG C, and 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 again that 0.1mol/L potassium hydroxide solution regulates pH=10, Keep agitation 4h, hold over night, suction filtration, spend deionized water more extremely without chlorion, at room temperature dry, then roasting reduction, calcination atmosphere is argon gas, sintering temperature is 200 DEG C, at the mist reductase 12 h that reducing agent is hydrogen and argon gas, reduction temperature is 200 DEG C, 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 again that 2mol/L sodium carbonate liquor regulates pH=10, Keep agitation 4h, hold over night, suction filtration, spend deionized water more extremely without chlorion, at room temperature dry, then roasting reduction, calcination atmosphere is argon gas, sintering temperature is 700 DEG C, with sodium borohydride reduction activation, reduction temperature is 20 DEG C, obtains bimetallic catalyst 5.
Embodiment 6(the present invention)
Ruthenium trichloride 120mg and nickel nitrate 600mg is dissolved in 50mL deionized water, is fully uniformly mixed, then add carrier 10g aluminium oxide, continue to keep 1h;
Add mass fraction 25% ammoniacal liquor again and regulate pH=9, Keep agitation 0.5h, hold over night, hold over night, suction filtration, then spend deionized water to without chlorion, at room temperature dry, then roasting reduction, calcination atmosphere is air, and sintering temperature is 200 DEG C, and reducing agent is ethylene glycol, reduction temperature is 80 DEG C, obtains bimetallic catalyst 6.
Embodiment 7(the present invention)
Ruthenium trichloride 120mg and nickel nitrate 600mg is dissolved in 50mL deionized water, is fully uniformly mixed, then add carrier 10g silica, continue to keep 5h;
Add mass fraction 10% urea liquid again and regulate pH=10, Keep agitation 5h, hold over night, suction filtration, then spend deionized water to without chlorion, at room temperature dry, hydrogen atmosphere reduction, reduction temperature is 700 DEG C, and hydrogen gas space velocity is 400h
-1, obtain bimetallic catalyst 7.
Embodiment 8(the present invention)
Be dissolved in 50mL deionized water by ruthenium trichloride 120mg and nickel nitrate 600mg, be fully uniformly mixed, then adding carrier is titanium dioxide 10g, continues to stir 10h;
Add the potassium alkaline solution adjustment pH=10 that concentration is 5mol/L again, Keep agitation 10h, hold over night, suction filtration, spend deionized water more extremely without chlorion, at room temperature dry, then roasting reduction, calcination atmosphere is air, sintering temperature is 400 DEG C, reducing agent is ethylene glycol, and reduction temperature is 100 DEG C, obtains bimetallic catalyst 8.
Embodiment 9(the present invention)
Ruthenium trichloride 60mg and nickel nitrate 250mg is dissolved in 50mL deionized water, is fully uniformly mixed, then add the mixture 10g that carrier is silica and aluminium oxide, continue to stir 24h;
Add the potassium alkaline solution adjustment pH=9 that concentration is 10mol/L again, Keep agitation 24h, hold over night, suction filtration, spend deionized water again to without chlorion, at room temperature dry, reduction activation, reducing agent is ethylene glycol, and reduction temperature is 100 DEG C, 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 add in 200mL autoclave successively, airtight, nitrogen purges three times, and then hydrogen purge once, is warming up to 65 DEG C, regulate hydrogen reaction pressure 8-10atm, open magnetic agitation, start reaction, when being zero to consumption hydrogen gas rate, reaction terminates, and reacted mixture adopts gas chromatographic analysis;
Table 1 reaction condition and catalyst activity evaluation result:
The result explanation that embodiment 3-10 catalyst activity is evaluated, by introducing the second metal component, adopt the bimetallic catalyst that absorption-deposition legal system is standby, can 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, bimetallic catalyst activity improves twice; When keeping equal catalytic activity, the use amount of noble metal can be reduced, reduce catalyst cost.
Claims (1)
1. the preparation method of the bimetallic catalyst of a synthesizing succinic acid dialkyl, it is characterized in that this catalyst is ruthenium and iron, nickel or copper by active component, carrier is aluminium oxide, silica, one or both compositions in titanium dioxide, the content of ruthenium is 0.1-5.0% by weight percentage, and the content of iron, nickel or copper is 0.5-20%, and the content of carrier is 99.4-75%, adopt 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 deionized water, be fully uniformly mixed, then adding carrier is aluminium oxide, silica, titanium dioxide, continues to stir 1-24h;
B, step a solution is added alkaline solution is ammoniacal liquor, urea liquid or concentration are the potassium hydroxide of 0.1-10mol/L, NaOH, potash or sodium carbonate liquor, regulate pH=9-10, Keep agitation 0.5-24h, hold over night, suction filtration, spend deionized water more extremely without chlorion, drying, then roasting reduction, wherein calcination atmosphere is argon gas or air, sintering temperature is 100-700 DEG C, reducing agent is the gaseous mixture of hydrogen, hydrogen and argon gas, sodium borohydride or ethylene glycol, and reduction temperature is 20-700 DEG C, obtains bimetallic catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102600836A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院新疆理化技术研究所 | Preparation method and application of catalyst for synthesizing dialkyl succinate |
| CN102863335A (en) * | 2012-10-15 | 2013-01-09 | 中国科学院长春应用化学研究所 | Preparation method of diethyl succinate |
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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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102600836A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院新疆理化技术研究所 | Preparation method and application of catalyst for synthesizing dialkyl succinate |
| CN102863335A (en) * | 2012-10-15 | 2013-01-09 | 中国科学院长春应用化学研究所 | Preparation method of diethyl succinate |
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