CN101700496A - Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof - Google Patents
Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof Download PDFInfo
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- CN101700496A CN101700496A CN200910184925A CN200910184925A CN101700496A CN 101700496 A CN101700496 A CN 101700496A CN 200910184925 A CN200910184925 A CN 200910184925A CN 200910184925 A CN200910184925 A CN 200910184925A CN 101700496 A CN101700496 A CN 101700496A
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Abstract
The invention discloses a catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and a preparation method thereof. The catalyst takes metal copper as a main active component, silver and manganese as auxiliary components and Al2O3 as a carrier, wherein the content of metal copper accounts for 25-50% of the mass of the catalyst, the content of metal silver accounts for 5-15% of the mass of the catalyst, the content of metal manganese accounts for 8-20%, and the content of Al2O3 accounts for 15-40% of the mass of the catalyst. In the reaction for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate, the catalyst of the invention has the advantages of high reaction activity, simple preparation method, easily obtained raw material resource, low price, lower cost and longer service life, the methyl glycolate has high selectivity, stable reaction performance and easy controllability.
Description
Technical field
The invention belongs to the catalyst chemical field, particularly a kind of Catalysts and its preparation method of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters.
Background technology
Methyl glycollate is a compound with α-H, hydroxyl and ester group functional group, therefore, oxonation, hydrolysis, oxidation reaction can take place in it, it is widely used in organic synthesis and medicine is synthetic, as the important chemical reaction intermediate: the large chemical products ethylene glycol of a. hydrogenating reduction system solves the raw material problem in short supply by the petroleum path preparing ethylene glycol; B. hydrolysis system glycolic is widely used as bactericide, chemical etc.; C. oxidative dehydrogenation system glyoxalic acid methylester, glyoxalic acid methylester hydrolysate glyoxalic acid is the primary raw material of synthesis of vanillin spices, medical allantoin, acetophenone etc.; D. ammonia is separated the system glycine, carbonylation system malonic acid (list) methyl esters.Simultaneously it still is a kind of fine solvent, can dissolving cellulos, resin, rubber etc.
At present, chloroactic acid method is mainly adopted in methyl glycollate production both at home and abroad, being about to monoxone mixes with caustic soda, the sodium chloride that removes the dereaction generation then obtains glycolic, and then adds methyl alcohol and strong sulfuric acid response generation methyl glycollate, and its production is seriously polluted, waste water is difficult to handle, the methyl glycollate concentration of producing is low, contains higher chlorion, has a strong impact in medicine and other fields and uses as intermediate.It is raw material that Mitsui east presses KCC to adopt glyoxal and methyl alcohol, with Al (NO
3)
39H
2O is a catalyst, reacts down at 160 ℃ to generate methyl glycollate, and owing to glyoxal costs an arm and a leg, so this flow process and uneconomical.Also have a kind of method be with formalin and CO under the situation that catalyst such as sulfuric acid or boron trifluoride exist, condensation generates glycolic under 70MPa and high temperature, reaction generates methyl glycollate with methyl alcohol again, and this reaction is owing to adopt HTHP, and actual production is very difficult.Therefore, methyl glycollate is invented a kind of environmental friendliness, also can be applicable to that the methyl glycollate production procedure of actual industrial production is then extremely important as a kind of important chemical product.
Summary of the invention
Technical problem
The object of the present invention is to provide a kind of environmental friendliness also can be applicable to the Catalysts and its preparation method that is used for dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters of high activity, high selectivity and the long service life of actual industrial production.
Technical scheme
The present invention is achieved by the following technical programs.
A kind of catalyst of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters, described catalyst is main active component with metallic copper, silver and manganese are for helping active component, Al
2O
3Be carrier; Wherein metallic copper content is 25%～50% of catalyst quality, and argent content is 5%～15% of catalyst quality, and manganese metal content is 8%～20% of catalyst quality, Al
2O
3Content is 15%～40% of catalyst quality.
The catalyst of above-mentioned a kind of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters, metallic copper content is 45% of catalyst quality, and argent content is 8% of catalyst quality, and manganese metal content is 12% of catalyst quality, Al
2O
3Content is 35% of catalyst quality.
The Preparation of catalysts method of above-mentioned a kind of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters comprises the steps: that (1) is with Al (OH)
3Powder and distilled water mix stirring, and are warming up to 50 ℃～80 ℃, constant temperature 15min～20min; (2) splash into Na again
2CO
3The aqueous solution drips time 20min～30min, then 60 ℃～80 ℃ of constant temperature and stir 20min～30min; (3) splash into the nitrate of metallic copper, the nitrate of argent and the nitrate of manganese metal and dissolve the mixed aqueous solution that is made into, drip time 40min～60min, 60 ℃～80 ℃ of dropping temperatures, dropping is used Na after finishing
2CO
3PH value=9～10 of aqueous solution regulation system; (4) mixed system that above-mentioned steps is made 70 ℃～80 ℃ stir 40min～60min after suction filtration, and use suction filtration behind the distilled water washing leaching cake repeatedly, stop washing leaching cake when when filtrate is detected with diphenylamines sulfuric acid liquid reagent, being colourless; (5) with filter cake at 110 ℃～130 ℃ dry 2h～3h, then at 300 ℃～400 ℃ calcining 2h～3h, and add that to account for catalyst quality percentage be that 0.8%～1% graphite carries out compressing tablet, finally make catalyst.
Beneficial effect
Catalyst of the present invention has very high reactivity in the reaction of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters, the selectivity of methyl glycollate is also very high.The Preparation of catalysts method is simple, and raw material sources are easy to get, and is cheap, and cost is lower, and the service life of catalyst is also longer simultaneously.A kind of eco-friendly production procedure that is applicable to the methyl glycollate of actual industrial production is provided, and reactivity worth is steady, is easy to control.
The specific embodiment
A kind of Preparation of catalysts method of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters comprises the steps: that (1) is with Al (OH)
3Powder and distilled water mix stirring, and are warming up to 50 ℃～80 ℃, constant temperature 15min～20min; (2) splash into Na again
2CO
3The aqueous solution drips time 20min～30min, then 60 ℃～80 ℃ of constant temperature and stir 20min～30min; (3) splash into the nitrate of metallic copper, the nitrate of argent and the nitrate of manganese metal and dissolve the mixed aqueous solution that is made into, drip time 40min～60min, 60 ℃～80 ℃ of dropping temperatures, dropping is used Na after finishing
2CO
3PH value=9～10 of aqueous solution regulation system; (4) mixed system that above-mentioned steps is made 70 ℃～80 ℃ stir 40min～60min after suction filtration, and use suction filtration behind the distilled water washing leaching cake repeatedly, stop washing leaching cake when when filtrate is detected with diphenylamines sulfuric acid liquid reagent, being colourless; (5) with filter cake at 110 ℃～130 ℃ dry 2h～3h, then at 300 ℃～400 ℃ calcining 2h～3h, and add that to account for catalyst quality percentage be that 0.8%～1% graphite carries out compressing tablet, finally make catalyst.
Embodiment 1
A kind of Preparation of catalysts method of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters comprises the steps: that (1) takes by weighing 30gAl (OH)
3Powder, fineness are 300 orders, add 1000ml distilled water and mix stirring, and be warming up to 65 ℃, constant temperature 15min; (2) splash into the Na that 100g concentration is 15wt% again
2CO
3The aqueous solution drips time 20min, then 65 ℃ of constant temperature and stir 20min; (3) take by weighing 160g Cu (NO
3)
26H
2O, 18g Mn (NO
3)
24H
2O and 5g AgNO
3Be dissolved in 600g distilled water and be made into mixed aqueous solution, and mixed aqueous solution is evenly splashed in the step 2 gained solution, drip time 40min, 70 ℃ of dropping temperatures, dripping the end back is the Na of 15wt% with concentration
2CO
3PH value=9 of aqueous solution regulation system; (4) mixed system that above-mentioned steps is made 75 ℃ stir 40min after suction filtration, and use suction filtration behind the distilled water washing leaching cake repeatedly, stop washing leaching cake when when filtrate is detected with diphenylamines sulfuric acid liquid reagent, being colourless; (5) with filter cake at 120 ℃ of dry 2.5h, then at 350 ℃ of calcining 2.5h, and add that to account for catalyst quality percentage be that 0.8% graphite carries out compressing tablet, be pressed into diameter 3mm, the cylinder shape catalyst of high 5mm makes catalyst A.
Embodiment 2
A kind of Preparation of catalysts method of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters comprises the steps: that (1) takes by weighing 30gAl (OH)
3Powder, fineness are 400 orders, add 1000ml distilled water and mix stirring, and be warming up to 50 ℃, constant temperature 18min; (2) splash into the Na that 110g concentration is 20wt% again
2CO
3The aqueous solution drips time 25min, then 80 ℃ of constant temperature and stir 30min; (3) take by weighing 180g Cu (NO
3)
26H
2O, 8g Mn (NO
3)
24H
2O and 8g AgNO
3Be dissolved in 700g distilled water and be made into mixed aqueous solution, and mixed aqueous solution is evenly splashed in the step 2 gained solution, drip time 60min, 60 ℃ of dropping temperatures, dripping the end back is the Na of 20wt% with concentration
2CO
3PH value=10 of aqueous solution regulation system; (4) mixed system that above-mentioned steps is made 80 ℃ stir 60min after suction filtration, and use suction filtration behind the distilled water washing leaching cake repeatedly, stop washing leaching cake when when filtrate is detected with diphenylamines sulfuric acid liquid reagent, being colourless; (5) with filter cake at 110 ℃ of dry 3h, then at 400 ℃ of calcining 2h, and add that to account for catalyst quality percentage be that 1% graphite carries out compressing tablet, be pressed into diameter 4mm, the cylinder shape catalyst of high 5mm makes catalyst B.
Embodiment 3
A kind of Preparation of catalysts method of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters comprises the steps: that (1) takes by weighing 30gAl (OH)
3Powder, fineness are 400 orders, add 1000ml distilled water and mix stirring, and be warming up to 80 ℃, constant temperature 20min; (2) splash into the Na that 115g concentration is 20wt% again
2CO
3The aqueous solution drips time 30min, then 60 ℃ of constant temperature and stir 25min; (3) take by weighing 170g Cu (NO
3)
26H
2O, 12g Mn (NO
3)
24H
2O and 6g AgNO
3Be dissolved in 650g distilled water and be made into mixed aqueous solution, and mixed aqueous solution is evenly splashed in the step 2 gained solution, drip time 50min, 80 ℃ of dropping temperatures, dripping the end back is the Na of 20wt% with concentration
2CO
3PH value=9.5 of aqueous solution regulation system; (4) mixed system that above-mentioned steps is made 70 ℃ stir 50min after suction filtration, and use suction filtration behind the distilled water washing leaching cake repeatedly, stop washing leaching cake when when filtrate is detected with diphenylamines sulfuric acid liquid reagent, being colourless; (5) with filter cake at 130 ℃ of dry 2h, then at 300 ℃ of calcining 3h, and add that to account for catalyst quality percentage be that 0.9% graphite carries out compressing tablet, be pressed into diameter 4mm, the cylinder shape catalyst of high 5mm makes catalyst C.
The catalyst performance test
It is 32mm that A, B and C are respectively got the 50g internal diameter of packing into, and in the stainless steel reactor of height 500mm, dimethyl oxalate and H2 mix the back and be warming up to 180 ℃ by conduction oil and enter in the reactor, 180 ℃～210 ℃ of temperature of reactor, pressure 1.0MPa, hydrogen ester be than 70, dimethyl oxalate charging air speed 0.4h
-1, after reaction was carried out 1000 hours continuously, catalyst activity was not seen reduction, reaction result sees the following form:
| Catalyst | Dimethyl oxalate conversion ratio % | Methyl glycollate selectivity % |
| ??A | ??96 | ??75 |
| ??B | ??98 | ??73 |
| ??C | ??98 | ??75 |
Claims (3)
1. the catalyst of a dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters is characterized in that, described catalyst is main active component with metallic copper, and silver and manganese are for helping active component, Al
2O
3Be carrier; Wherein metallic copper content is 25%～50% of catalyst quality, and argent content is 5%～15% of catalyst quality, and manganese metal content is 8%～20% of catalyst quality, Al
2O
3Content is 15%～40% of catalyst quality.
2. the catalyst of a kind of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters as claimed in claim 1 is characterized in that, metallic copper content is 45% of catalyst quality, and argent content is 8% of catalyst quality, and manganese metal content is 12% of catalyst quality, Al
2O
3Content is 35% of catalyst quality.
3. the Preparation of catalysts method of a kind of dimethyl oxalate hydrogenation synthesizing of glycolate methyl esters as claimed in claim 1 is characterized in that, comprises the steps: that (1) is with Al (OH)
3Powder and distilled water mix stirring, and are warming up to 50 ℃～80 ℃, constant temperature 15min～20min; (2) splash into Na again
2CO
3The aqueous solution drips time 20min～30min, then 60 ℃～80 ℃ of constant temperature and stir 20min～30min; (3) splash into the nitrate of metallic copper, the nitrate of argent and the nitrate of manganese metal and dissolve the mixed aqueous solution that is mixed with, drip time 40min～60min, 60 ℃～80 ℃ of dropping temperatures, dropping is used Na after finishing
2CO
3PH value=9～10 of aqueous solution regulation system; (4) mixed system that above-mentioned steps is made 70 ℃～80 ℃ stir 40min～60min after suction filtration, and use suction filtration behind the distilled water washing leaching cake repeatedly, stop washing leaching cake when when filtrate is detected with diphenylamines sulfuric acid liquid reagent, being colourless; (5) with filter cake at 110 ℃～130 ℃ dry 2h～3h, then at 300 ℃～400 ℃ calcining 2h～3h, and add that to account for catalyst quality percentage be that 0.8%～1% graphite carries out compressing tablet, finally make catalyst.
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|---|---|---|---|
| CN2009101849255A CN101700496B (en) | 2009-10-21 | 2009-10-21 | Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101849255A CN101700496B (en) | 2009-10-21 | 2009-10-21 | Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof |
Publications (2)
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|---|---|
| CN101700496A true CN101700496A (en) | 2010-05-05 |
| CN101700496B CN101700496B (en) | 2012-03-07 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954288A (en) * | 2010-09-27 | 2011-01-26 | 上海华谊（集团）公司 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
| CN102001944A (en) * | 2010-10-27 | 2011-04-06 | 上海华谊（集团）公司 | Method for preparing glycolate by catalyzing oxalate under action of hydrogenation |
| CN102649742A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for increasing selectivity of glycollic acid ester |
| CN102649072A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Fluidized bed catalyst of glycolate catalyzed from oxalic ester |
| CN105251521A (en) * | 2015-11-19 | 2016-01-20 | 中科合成油淮南催化剂有限公司 | Loaded type transition metal phosphide catalyst as well as preparation method and application thereof |
| CN110142048A (en) * | 2019-06-11 | 2019-08-20 | 宁波中科远东催化工程技术有限公司 | A kind of silver-bearing copper catalyst for Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and preparation method thereof and application method |
| CN116273008A (en) * | 2023-03-28 | 2023-06-23 | 江苏金聚合金材料有限公司 | Preparation method and application of methyl glycolate catalyst |
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| CN101185888B (en) * | 2007-12-04 | 2011-08-31 | 南京工业大学 | Catalyst for inducing catalytic oxidation technique and preparation method thereof |
| CN101422739B (en) * | 2008-11-03 | 2011-12-14 | 大连大学 | Diatomic alcohol load type catalyst by glycerol hydrogenolysis and preparation method thereof |
| CN101474566B (en) * | 2009-01-05 | 2012-02-01 | 东南大学 | Integral catalyst for catalytic combustion of toluol exhaust gas and preparation method thereof |
| CN101524646A (en) * | 2009-04-16 | 2009-09-09 | 丹阳市丹化金煤化工有限公司 | Glycol catalyst synthesized by hydrogenating oxalic ester and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954288A (en) * | 2010-09-27 | 2011-01-26 | 上海华谊（集团）公司 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
| CN101954288B (en) * | 2010-09-27 | 2013-01-23 | 上海华谊（集团）公司 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
| CN102001944A (en) * | 2010-10-27 | 2011-04-06 | 上海华谊（集团）公司 | Method for preparing glycolate by catalyzing oxalate under action of hydrogenation |
| CN102001944B (en) * | 2010-10-27 | 2014-05-14 | 上海华谊（集团）公司 | Method for preparing glycolate by catalyzing oxalate under action of hydrogenation |
| CN102649742A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for increasing selectivity of glycollic acid ester |
| CN102649072A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Fluidized bed catalyst of glycolate catalyzed from oxalic ester |
| CN102649072B (en) * | 2011-02-25 | 2014-05-28 | 中国石油化工股份有限公司 | Fluidized bed catalyst of glycolate catalyzed from oxalic ester |
| CN102649742B (en) * | 2011-02-25 | 2015-01-07 | 中国石油化工股份有限公司 | Method for increasing selectivity of glycollic acid ester |
| CN105251521A (en) * | 2015-11-19 | 2016-01-20 | 中科合成油淮南催化剂有限公司 | Loaded type transition metal phosphide catalyst as well as preparation method and application thereof |
| CN110142048A (en) * | 2019-06-11 | 2019-08-20 | 宁波中科远东催化工程技术有限公司 | A kind of silver-bearing copper catalyst for Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and preparation method thereof and application method |
| CN116273008A (en) * | 2023-03-28 | 2023-06-23 | 江苏金聚合金材料有限公司 | Preparation method and application of methyl glycolate catalyst |
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