CN103785408B - A kind of prepared by dimethyl oxalate plus hydrogen is for catalyst and the synthetic method of methyl glycollate - Google Patents
A kind of prepared by dimethyl oxalate plus hydrogen is for catalyst and the synthetic method of methyl glycollate Download PDFInfo
- Publication number
- CN103785408B CN103785408B CN201410048657.5A CN201410048657A CN103785408B CN 103785408 B CN103785408 B CN 103785408B CN 201410048657 A CN201410048657 A CN 201410048657A CN 103785408 B CN103785408 B CN 103785408B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hours
- temperature
- dimethyl oxalate
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses catalyst and the synthetic method of a kind of prepared by dimethyl oxalate plus hydrogen for methyl glycollate, belong to methyl glycollate catalyst preparation technical field. Described catalyst is all prepared from as precipitating reagent with NaOH, the main active component that wherein Cu is catalyst, taking alkaline silica sol as carrier, contain one or more base metals in Mn, Zr, Zn as auxiliary agent simultaneously, wherein metallic copper mass content is 10% ~ 40%, other base metal auxiliary agent content are 5% ~ 10%, and vector contg is 60% ~ 80%. Method for preparing catalyst of the present invention is simple, cheap and easy to get, prepares reproduciblely, and catalyst has showed higher reactivity at prepared by dimethyl oxalate plus hydrogen in methyl glycollate reaction, and catalyst stability and methyl glycollate is selectively all higher.
Description
Technical field
The present invention relates to the process for synthetic catalyst of a kind of prepared by dimethyl oxalate plus hydrogen for methyl glycollate, belong to methyl glycollate catalyst preparation technical field.
Technical background
Methyl glycollate (MG) is the simplest class carboxylic ester, that current high-end agricultural chemicals, medicine, chemical industry environmental protection field are needed chemicals badly, the fine solvent of synthetic cellulose, rubber, resin etc., and the anti-carrier additives raw material of more synthetic raising lubricating oil extreme pressures and wearability. In addition, methyl glycollate is a compound simultaneously with hydroxyl, carbonyl and α-H functional group, can prepare a series of important downstream product as intermediate, as prepared by hydrolysis, glycolic, Hydrogenation are prepared dimethyl malenate for ethylene glycol, carbonylation and ethyl acetoacetate, ammonia solution are prepared DL-glycine, glyoxylic ester etc. is prepared in oxidative dehydrogenation.
The prior synthesizing method of methyl glycollate has a lot, and most Shortcomings in these traditional handicrafts, for example glyoxal and methyl alcohol one-step synthesis are prepared MG, and the glyoxal toxicity in raw material is too large, and price is high, is not suitable for suitability for industrialized production; Formaldehyde and hydrogen cyanide addition process, feed hydrogen cyanic acid has severe toxicity, is also not suitable for large-scale production even if yield is higher; Coupling method, adopts liquid and solid strong acid catalysis mostly, has the defect that serious corrosion and reaction pressure are high. At present, adopt the method for chloracetic acid hydrolysis resterification in China more, have the problems such as corrosion is heavy, pollution is heavy, raw material is limited, need the methyl glycollate production line of economy of exploitation, environmental protection, sustainable development badly.
China's energy resource structure " rich coal, oil starvation, weak breath ", 2.3% of the oil workable reserves Jin Zhan world, exceed 50% to international petroleum is interdependent, but coal resources are very abundant, make full use of the coal resources of China's abundant, walk coal through carbonizer's processes such as synthesis gas, synthetic fuel or product have obvious economic worth and great strategic significance.
From existing document, in reaction at prepared by dimethyl oxalate plus hydrogen for methyl glycollate, most of catalyst has used and has added the copper-based catalysts (CN101954288 after the modified with noble metals such as Ag, Au, Pt and Ru, CN101700496), can make object product methyl glycollate selectively greatly improve, but the interpolation of noble metal has increased the production cost of catalyst, if can make auxiliary agent with base metal, can reduce Catalyst Production cost.
Summary of the invention
The object of this invention is to provide the preparation method of clean, inexpensive, the simple and easy to get Hydrogenation of Dimethyl Oxalate catalyst of a kind of green.
Technical scheme of the present invention is:
Prepared by dimethyl oxalate plus hydrogen is for a catalyst for methyl glycollate, and it is taking metallic copper as main active component, and one or more base metals of zirconium, zinc and manganese are auxiliary agent, SiO2For carrier; Wherein metallic copper content is 10% ~ 40%, preferably 10% ~ 20%; Non-metal assistant content is 2% ~ 10%, preferably 4% ~ 8%; All the other are carrier S iO2。
Wherein said prepared by dimethyl oxalate plus hydrogen, for the preparation method of the catalyst of methyl glycollate, carries out according to following step:
(1) by copper nitrate with contain a kind of nitrate precursor deionized water dissolving in the metal ions such as Zr, Zn or Mn.
(2) according to adding auxiliary agent kind, add NaOH and Cu2+，Mn2+，Zn2+，Zr4+Mol ratio be respectively 2:1,2:1,2:1,4:1, and be made into the solution that concentration is 2mol/L with deionized water dissolving.
(3), under agitating heating state, the solution of step 1) preparation is added to step 2) in the solution of preparation, until pH is about 8.0.
(4) alkaline silica sol is added in the solution of step 3) gained, and stir 4 ~ 8 hours at 80 ~ 100 DEG C, then under said temperature, leave standstill aging 8 ~ 18 hours. Wherein reaction temperature is preferably 80 DEG C, and reaction mixing time is preferably 4 hours, and ageing time is preferably 12 hours.
(5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 400 ~ 600 DEG C of roastings 3 ~ 8 hours in Muffle furnace, make catalyst precursor. Wherein Muffle furnace sintering temperature is preferably 450 DEG C, roasting time preferably 4 hours. Catalyst after roasting is carried out to compression molding, and the certain order of cutting screening is counted 20mL.
The present invention can catalysis prepared by dimethyl oxalate plus hydrogen for methyl glycollate, the catalyst preparation process that reacts required is simple, low price, the catalyst of preparation is reproducible; While being applied to this reaction, catalyst activity and stability are higher, and the selective height of methyl glycollate. Wherein, under certain reaction temperature, dimethyl oxalate conversion ratio can reach 86%, and methyl glycollate selectively can reach 81%.
Detailed description of the invention
Embodiment 1
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 11.40gCu (NO3)2.3H2Mn (the NO that O and 6.25g mass fraction are 50%3)2.6H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH4.65g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 10%Cu-2%Mn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure; Maintain 2.0MPa at system pressure, temperature is under 210 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 25:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 81.6%, methyl glycollate be selectively 69.5%.
Embodiment 2
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 11.40gCu (NO3)2.3H2Zn (the NO of O and 2.73g3)2.3H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH4.51g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 10%Cu-2%Zn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure; Maintain 2.0MPa at system pressure, temperature is under 230 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 30:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 82.3%, methyl glycollate be selectively 71.4%.
Embodiment 3
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 11.40gCu (NO3)2.3H2The ZrOCl of O and 2.12g2.8H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH4.83g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 10%Cu-2%Zr/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure; Maintain 2.0MPa at system pressure, temperature is under 220 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 30:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 80.1%, methyl glycollate be selectively 70.2%.
Embodiment 4
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 11.40gCu (NO3)2.3H2Mn (the NO of O and 31.25g50%3)2.6H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH8.14g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 10%Cu-10%Mn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 220 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 25:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 82.1%, methyl glycollate be selectively 71.5%.
Embodiment 5
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 11.40gCu (NO3)2.3H2Zn (the NO of O and 13.65g3)2.3H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH7.45g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 10%Cu-10%Zn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 230 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 20:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 83.3%, methyl glycollate be selectively 73.1%.
Embodiment 6
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 11.40gCu (NO3)2.3H2The ZrOCl of O and 10.60g2.8H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH9.04g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 10%Cu-10%Zr/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 220 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 30:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 88.6%, methyl glycollate be selectively 74.5%.
Embodiment 7
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 45.62gCu (NO3)2.3H2Mn (the NO that O and 6.25g mass fraction are 50%3)2.6H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH15.98g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 40%Cu-2%Mn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure; Maintain 2.0MPa at system pressure, temperature is under 210 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 25:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 82.7%, methyl glycollate be selectively 70.2%.
Embodiment 8
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 45.62gCu (NO3)2.3H2Zn (the NO of O and 2.73g3)2.3H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH15.84g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 40%Cu-2%Zn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure; Maintain 2.0MPa at system pressure, temperature is under 230 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 30:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 83.1%, methyl glycollate be selectively 73.8%.
Embodiment 9
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 45.62gCu (NO3)2.3H2The ZrOCl of O and 2.12g2.8H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH16.16g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 40%Cu-2%Zr/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure; Maintain 2.0MPa at system pressure, temperature is under 220 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 30:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 81.2%, methyl glycollate be selectively 71.1%.
Embodiment 10
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 45.62gCu (NO3)2.3H2Mn (the NO of O and 31.25g50%3)2.6H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH19.48g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 40%Cu-10%Mn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 220 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 25:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 85.1%, methyl glycollate be selectively 73.5%.
Embodiment 11
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 45.62gCu (NO3)2.3H2Zn (the NO of O and 13.65g3)2.3H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH18.78g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 40%Cu-10%Zn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 230 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 20:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 79.8%, methyl glycollate be selectively 70.7%.
Embodiment 12
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 45.62gCu (NO3)2.3H2The ZrOCl of O and 10.60g2.8H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH20.36g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 40%Cu-10%Zr/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 220 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 30:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 84.2%, methyl glycollate be selectively 73.3%.
Embodiment 13
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 18.25gCu (NO3)2.3H2Mn (the NO of O and 25g50%3)2.6H2O, and use 200mL deionized water dissolving; (2), according to metal ion content, take and can make NaOH11.05g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 24 ~ 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 16%Cu-8%Mn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 220 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 30:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 88.6%, methyl glycollate be selectively 74.5%.
Embodiment 14
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 18.25gCu (NO3)2.3H2O and 7.42gZrOCl2.8H2O, and use 200mL deionized water dissolving; (2), according to metal ion content, take and can make NaOH11.24g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 24 ~ 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 16%Cu-7%Zr/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 250 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 25:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 86.9%, methyl glycollate be selectively 84.5%.
Embodiment 15
A kind of prepared by dimethyl oxalate plus hydrogen is for the process for synthetic catalyst of methyl glycollate: comprise the steps: that (1) takes about 18.25gCu (NO3)2.3H2Zn (the NO of O and 5.46g3)2.3H2O, and use 200mL deionized water dissolving; (2), according to metal ion content, take and can make NaOH7.79g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) stirring and bath temperature is under 80 DEG C of states, the nitrate solution of step 1) preparation be slowly added dropwise to step 2) in the NaOH solution of preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step 3) gained, and stir 4 hours at this temperature, then under said temperature, leave standstill aging 12 hours. (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 24 ~ 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor. (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers. Component in gained catalyst is 16%Cu-4%Zn/SiO2。
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 250 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 30:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 85.8%, methyl glycollate be selectively 83.6%.
Above example is only for illustrating content of the present invention, and in addition, the present invention also has other embodiment. But being equal to, all employings replace or the technical scheme that forms of equivalent deformation mode all drops in protection scope of the present invention.
Claims (3)
1. prepared by dimethyl oxalate plus hydrogen, for a preparation method for the catalyst of methyl glycollate, carries out according to following step:
(1) take about 11.40gCu (NO3)2·3H2Mn (the NO of O and 31.25g50%3)2·6H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH8.14g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) be under 80 DEG C of states in stirring and bath temperature, the nitrate solution of step (1) preparation is slowly added dropwise in the NaOH solution of step (2) preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step (3) gained, and at this temperature, stir 4 hours, then under said temperature, leave standstill aging 12 hours; (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor; (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers; Component in gained catalyst is 10%Cu-10%Mn/SiO2；
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 220 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 25:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 82.1%, methyl glycollate be selectively 71.5%.
2. prepared by dimethyl oxalate plus hydrogen, for a preparation method for the catalyst of methyl glycollate, carries out according to following step: (1) takes about 11.40gCu (NO3)2·3H2Zn (the NO of O and 13.65g3)2·3H2O, and use 200mL deionized water dissolving; (2) take and can make NaOH7.45g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) be under 80 DEG C of states in stirring and bath temperature, the nitrate solution of step (1) preparation is slowly added dropwise in the NaOH solution of step (2) preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step (3) gained, and at this temperature, stir 4 hours, then under said temperature, leave standstill aging 12 hours; (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor; (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers; Component in gained catalyst is 10%Cu-10%Zn/SiO2；
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 230 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 20:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 83.3%, methyl glycollate be selectively 73.1%.
3. prepared by dimethyl oxalate plus hydrogen, for a preparation method for the catalyst of methyl glycollate, carries out according to following step: (1) takes about 18.25gCu (NO3)2·3H2O and 7.42gZrOCl2·8H2O, and use 200mL deionized water dissolving; (2), according to metal ion content, take and can make NaOH11.24g that metal ion precipitates completely as precipitating reagent, and be made into the concentration of 2mol/L with deionized water dissolving; (3) be under 80 DEG C of states in stirring and bath temperature, the nitrate solution of step (1) preparation is slowly added dropwise in the NaOH solution of step (2) preparation, until pH is about 8.0, process is about 1 hour; (4) accelerate to stir, at the same temperature, alkaline silica sol is added in the solution of step (3) gained, and at this temperature, stir 4 hours, then under said temperature, leave standstill aging 12 hours; (5) by the catalyst suction filtration after aging, with deionized water washing for several times to filtrate pH be 7.0; Then filter cake is dried to 24 ~ 48 hours; The catalyst of oven dry is milled into powder, then 450 DEG C of roastings 4 hours in Muffle furnace, make catalyst precursor; (6) catalyst after roasting is carried out to compression molding, and the catalyst 20mL of cutting screening 20 ~ 40 order numbers; Component in gained catalyst is 16%Cu-7%Zr/SiO2；
By above-mentioned Catalyst packing fixed bed reactors, be 2.0MPa, temperature logical hydrogen reducing 4 hours while being 200 DEG C at system pressure, and maintain 2.0MPa at system pressure, temperature is under 250 DEG C of conditions, dimethyl oxalate liquid hourly space velocity (LHSV) is 1.0h-1, the raw mixture that hydrogen ester mol ratio is 25:1 reacts, reactant adopt gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 86.9%, methyl glycollate be selectively 84.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410048657.5A CN103785408B (en) | 2014-02-12 | 2014-02-12 | A kind of prepared by dimethyl oxalate plus hydrogen is for catalyst and the synthetic method of methyl glycollate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410048657.5A CN103785408B (en) | 2014-02-12 | 2014-02-12 | A kind of prepared by dimethyl oxalate plus hydrogen is for catalyst and the synthetic method of methyl glycollate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103785408A CN103785408A (en) | 2014-05-14 |
| CN103785408B true CN103785408B (en) | 2016-05-04 |
Family
ID=50661714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410048657.5A Active CN103785408B (en) | 2014-02-12 | 2014-02-12 | A kind of prepared by dimethyl oxalate plus hydrogen is for catalyst and the synthetic method of methyl glycollate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103785408B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435797B (en) * | 2014-08-27 | 2018-09-14 | 中国石油化工股份有限公司 | Carboxylic ester hydrogenation catalyst |
| CN108017511B (en) * | 2017-08-04 | 2021-01-08 | 华东理工大学 | Method for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
| CN110871071B (en) * | 2018-09-04 | 2022-02-01 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methyl glycolate and preparation and application thereof |
| CN111097426B (en) * | 2019-12-30 | 2022-08-30 | 天津市长芦化工新材料有限公司 | Copper-based gas phase catalyst and preparation method and application thereof |
| CN111672516B (en) * | 2020-07-14 | 2023-04-28 | 成都中科凯特科技有限公司 | Refining catalyst for polymethoxy dimethyl ether condensation product and preparation method thereof |
| CN113398983A (en) * | 2021-06-15 | 2021-09-17 | 中石化南京化工研究院有限公司 | Catalyst for preparing methyl glycolate by dimethyl oxalate hydrogenation and preparation method thereof |
| CN113600186A (en) * | 2021-09-09 | 2021-11-05 | 濮阳圣恺环保新材料科技股份有限公司 | Preparation method of copper-based hydrogenation catalyst with high mechanical strength |
| CN113893853B (en) * | 2021-09-28 | 2023-11-03 | 江苏金聚合金材料有限公司 | Composite carrier bimetallic ester hydrogenation catalyst and preparation method and application thereof |
| CN113797931B (en) * | 2021-09-29 | 2024-03-22 | 中触媒新材料股份有限公司 | Dimethyl oxalate hydrogenation catalyst, preparation method and application thereof |
| CN114029053B (en) * | 2021-11-22 | 2023-04-18 | 中国科学院大连化学物理研究所 | Preparation method of supported catalyst and application of supported catalyst in preparation of methyl glycolate from ethylene glycol |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440873A (en) * | 1981-04-30 | 1984-04-03 | Ube Industries, Ltd. | Process for producing ethylene glycol and/or glycolic acid ester, catalyst composition used therefor, and process for production thereof |
| 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 |
| CN102151568A (en) * | 2011-01-30 | 2011-08-17 | 山东华鲁恒升集团德化设计研究有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
-
2014
- 2014-02-12 CN CN201410048657.5A patent/CN103785408B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440873A (en) * | 1981-04-30 | 1984-04-03 | Ube Industries, Ltd. | Process for producing ethylene glycol and/or glycolic acid ester, catalyst composition used therefor, and process for production thereof |
| 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 |
| CN102151568A (en) * | 2011-01-30 | 2011-08-17 | 山东华鲁恒升集团德化设计研究有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103785408A (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103785408B (en) | A kind of prepared by dimethyl oxalate plus hydrogen is for catalyst and the synthetic method of methyl glycollate | |
| CN110711588B (en) | Application of hydrotalcite-based catalyst in conversion of high-concentration sugar to 1, 2-propylene glycol | |
| CN103193736A (en) | Method for synthesizing gamma-valerolactone based on catalytic hydrogenation | |
| CN103657658B (en) | Carboxylic ester hydrogenation catalyst and prepare the method for cyclohexanol and ethanol | |
| CN103372453B (en) | Catalyst for synthesis of methyl glycolate and preparation method thereof | |
| CN102218320A (en) | Catalyst for hydrogenation, preparation method and application thereof | |
| CN105498756B (en) | The catalyst of hydrogenation of carbon dioxide methanol | |
| CN101549292A (en) | Catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and preparing method thereof | |
| CN102091624A (en) | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof | |
| CN112755996A (en) | Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application | |
| CN106238051A (en) | Catalyst for ethyl acetate preparation of ethanol by hydrogenating and its preparation method and application | |
| JP2014189498A (en) | Method for producing lactic acid | |
| CN104190417B (en) | Preparation method of ruthenium-based bimetallic catalyst for preparing cyclohexene by partial hydrogenation of benzene | |
| CN104923218A (en) | Catalyst for itaconic acid hydrogenation as well as preparation method and use of catalyst, and method for preparing high value-added products from itaconic acid | |
| CN104525219A (en) | Method for preparing catalyst for preparing methyl glycolate by adding hydrogen into dimethyl oxalate | |
| CN112221509B (en) | Preparation method of high-stability methanol synthesis catalyst | |
| CN106944050B (en) | A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol | |
| CN111135828B (en) | Catalyst and application, preparation and performance test method of catalyst | |
| CN102836711B (en) | Catalyst for preparing cyclohexene via selective hydrogenation of benzene and preparation method thereof | |
| CN101428226A (en) | Selective hydrogenation catalyst for fine purification of p-benzene dicarboxylic acid | |
| CN102716751A (en) | Supported catalyst for hydrogen production by methanol reforming as well as preparation method and application thereof | |
| CN103191732A (en) | Method for preparing cyclohexene catalyst through partial hydrogenation of benzene, and method for producing cyclohexene through using cyclohexene catalyst | |
| CN102258994B (en) | Method for preparing catalyst used in synthesizing isophorone through acetone multiphase method | |
| CN104190424A (en) | Catalyst for preparing methyl ethyl ketone by dehydrogenation of sec-butyl alcohol and preparation method of catalyst | |
| CN101745396B (en) | Catalyst for preparing succinic acid dialkyl ester and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |