CN102380381A - Nanometer ultrafine glycol copper silicon catalyst and its preparation method - Google Patents
Nanometer ultrafine glycol copper silicon catalyst and its preparation method Download PDFInfo
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- CN102380381A CN102380381A CN2011102668199A CN201110266819A CN102380381A CN 102380381 A CN102380381 A CN 102380381A CN 2011102668199 A CN2011102668199 A CN 2011102668199A CN 201110266819 A CN201110266819 A CN 201110266819A CN 102380381 A CN102380381 A CN 102380381A
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Abstract
The invention discloses a nanometer ultrafine glycol copper silicon catalyst. According to the invention, silica sol is used as a carrier, Cu(NO3)2 is used as a predecessor and urea is used as a precipitating agent. During the preparation process, 1-30kHz supersonic wave is used to treat the solution. The catalyst provided by the invention has a nanometer ultrafine particle effect, high specific surface and high catalytic activity within a certain temperature and pressure range. The catalyst is used in the production of glycol by dimethyl oxalate and hydrogen to greatly raise the reaction rate and yield.
Description
Technical field the invention belongs to copper Si catalyst preparing technical field, relates to a kind of nano level superfine ethylene glycol copper Si catalyst and preparation method thereof.
Background technology is present; On the commercial production with dimethyl oxalate and Preparation of Hydrogen ethylene glycol; Reaction rate and productive rate are all lower, can not satisfy the demand of society to ethylene glycol, need demand developing the catalyst that can improve with dimethyl oxalate and Preparation of Hydrogen glycol reaction speed and productive rate urgently.
Summary of the invention the purpose of this invention is to provide a kind of nano level superfine ethylene glycol copper Si catalyst and preparation method thereof, in order to solve prior art with dimethyl oxalate and Preparation of Hydrogen ethylene glycol, the technical problem that reaction rate and productive rate are all lower.
Nano level superfine ethylene glycol copper Si catalyst of the present invention, it is that the Ludox of 10～20nm is a carrier with particle diameter, Cu (NO
3)
2.3H
2O is a predecessor, adopts (NH
2)
2CO is a precipitating reagent, is prepared from through deposition, adopts 1～30kHz ultrasonic wave that solution is handled in the precipitation process, and the mass ratio of each component is following:
Cu (NO
3)
2.3H
2O 72.48g (NH
2)
2CO 54.54g 25%SiO
2.H
2O Ludox 209.40g
The preparation method of nano level superfine ethylene glycol copper Si catalyst of the present invention, its main points are to be undertaken by following step:
1), with deionized water with 72.48gCu (NO
3)
2.3H
2O fully is dissolved in the beaker of 1000ml, is configured to the copper nitrate solution of 500ml; With deionized water with 54.54g (NH
2)
2CO fully is dissolved in the beaker of 1000ml, is configured to the urea liquid of 500ml; Accurately take by weighing 209.40g 25%SiO
2.H
2O in the beaker of 500ml, and adds an amount of HNO
3, it is 4 silicon sol solution that solution is transferred to the pH value, to prevent generating deposition when mixing with copper nitrate solution;
2), copper nitrate solution, urea liquid and silicon sol solution are poured in the beaker of 2000ml; And mix; Hold the beaker of copper nitrate solution, urea liquid and silicon sol solution then respectively with the washed with de-ionized water of 50ml; Pour in the 2000ml beaker that fills copper nitrate, urea and Ludox mixed solution, use HNO
3The pH value of mixed solution is transferred to 2, with deionized water mixed solution is diluted to 1500ml then;
3), in being poured into, mixed solution adorns in the flask of 1～30kHz supersonic generator and agitator; And turn on agitator; Stir 60min; Solution is mixed; Heating then; And open supersonic generator solution is handled, keeping simultaneously stirring and finish up to reaction, reaction temperature is controlled at 95～100 ℃;
4), stirring reaction 24 hours, detect the pH value of solution with pH meter, reach at 6.8 ± 0.2 o'clock, the reaction end stops heating, stirring and ultrasonic Treatment;
5), will react the sediment washing accomplished 2～3 times, use absolute ethanol washing again 1～2 time with 50～60 ℃ of hot deionized waters;
6), the deposition that will wash after accomplishing changes in the drying box, dried deposition is broken, sieve at 120 ℃ of dry 12h down, the adding mass percent is 1～10 ‰ stearic acid in the sieve powder, mixes, compression molding again;
7), the product behind the compression molding is changed over to carry out roasting in the roaster; Temperature programming is adopted in roasting: initial temperature is 20 ℃; After 30 minutes, rise to 120 ℃ 120 ℃ of insulations 120 minutes, rose to 200 ℃ again through 60 minutes, rose to 300 ℃ again through 300 minutes 300 ℃ of insulations 120 minutes 200 ℃ of insulations 150 minutes; Rise to 450 ℃ again through 450 minutes 450 ℃ of insulations 300 minutes, change reduction furnace over to after coming out of the stove;
8), the flow velocity with per minute 100ml feeds hydrogen to reduction furnace; Temperature programmed reduction is 14 hours in the atmosphere of pure hydrogen; The temperature programmed reduction process is: initial temperature is 180 ℃, after 2 hours, rises to 220 ℃ 220 ℃ of insulations 14 hours, has both got the copper Si catalyst.
Catalyst of the present invention has the nano level superfine particle effect, has than high-ratio surface, in certain temperature and pressure scope, advantages of high catalytic activity is arranged, and is used for dimethyl oxalate and the production of Preparation of Hydrogen ethylene glycol, has improved reaction rate and productive rate greatly.
Appended drawings is catalyst electron-microscope scanning figure of the present invention.
The specific embodiment prepares that nano level superfine ethylene glycol copper Si catalyst of the present invention is raw materials used to be had:
1, Cu (NO
3)
2.3H
2The O chemically pure reagent
2, (NH
2)
2The CO chemically pure reagent
3,25%SiO
2.H
2The O catalyst is used Ludox
Concrete technological operation step:
1, with deionized water with 72.48gCu (NO
3)
2.3H
2O fully is dissolved in the beaker of 1000ml, is configured to the Cu (NO of 500ml
3)
2Solution;
2, with deionized water with 54.54g (NH
2)
2CO fully is dissolved in the beaker of 1000ml, is configured to (the NH of 500ml
2)
2CO solution;
3, accurately take by weighing 209.40g 25%SiO
2.H
2O in the beaker of 500ml, and adds an amount of HNO
3, it is 4 that solution is transferred to pH value;
4, with Cu (NO
3)
2. solution, (NH
2)
2CO solution and SiO
2.H
2O solution is poured in the beaker of 2000ml, and mixes, and holds Cu (NO with the washed with de-ionized water of 50ml respectively then
3)
2. solution, (NH
2)
2CO solution and SiO
2.H
2The beaker of O solution is poured in the mixed solution beaker of 2000ml, uses HNO
3The pH value of mixed solution is transferred to 2, with deionized water mixed solution is diluted to 1500ml then;
5, mixed solution is poured in the flask of interior dress 15kHz supersonic generator and agitator; And turn on agitator, stir 60min, solution is mixed; Heat with electrical heating then; And open supersonic generator solution is handled, keeping simultaneously stirring and finish up to reaction, reaction temperature is controlled at 98 ℃;
6, stirring reaction is 24 hours, detects the pH value of solution with pH meter, reaches 6.8 ± 0.2 time reaction end, stops heating, stirring and ultrasonic Treatment;
7, will react the sediment washing accomplished 3 times with the deionized water of 55 ℃ of heat, absolute ethanol washing is 2 times again;
8, the deposition that will wash after accomplishing changes in the drying box, and 120 ℃ of dry 12h down are broken with dried deposition, sieve, and adds that to sieve the powder mass ratio be that 10 ‰ stearic acid mixes, again compression molding;
9, the catalyst behind the compression molding is changed over to carry out roasting in the roaster.Temperature programming is adopted in roasting;
10, (100ml H in the atmosphere of pure hydrogen
2/ min) temperature programmed reduction 14 hours, both copper Si catalyst of the present invention, the temperature programmed reduction process is:
In order to further specify specific surface performance of the present invention and applicable cases, see table 1 with table 2:
Table 1: catalyst specific surface is measured the result
| Sample number into spectrum | Measure result (m 2/g) |
| 1 | 387.8 |
| 2 | 341.1 |
| 3 | 354.0 |
Table 2: the copper Si catalyst is used for the dimethyl oxalate hydrogenation and produces ethylene glycol and accessory substance situation
Other conditions: P=1.9MPa H
2/ DMO=100 LHSV=1.0g/h/g-cat
25%SiO involved in the present invention
2.H
2The O Ludox is that average grain diameter is 10～20nmJN-25 Ludox.
Claims (2)
1. nano level superfine ethylene glycol copper Si catalyst, it is that the Ludox of 10～20nm is a carrier with particle diameter, Cu (NO
3)
2.3H
2O is a predecessor, adopts (NH
2)
2CO is a precipitating reagent, is prepared from through deposition, adopts 1～30kHz ultrasonic wave that solution is handled in the precipitation process, it is characterized in that the mass ratio of each component is following:
Cu (NO
3)
2.3H
2O 72.48g (NH
2)
2CO 54.54g 25%SiO
2.H
2OLudox 209.40g
2. the preparation method of nano level superfine ethylene glycol copper Si catalyst according to claim 1 is characterized in that being undertaken by following step:
1), with deionized water with 72.48gCu (NO
3)
2.3H
2O fully is dissolved in the beaker of 1000ml, is configured to the copper nitrate solution of 500ml; With deionized water with 54.54g (NH
2)
2CO fully is dissolved in the beaker of 1000ml, is configured to the urea liquid of 500ml; Accurately take by weighing 209.40g 25%SiO
2.H
2O in the beaker of 500ml, and adds an amount of HNO
3, it is 4 silicon sol solution that solution is transferred to the pH value;
2), copper nitrate solution, urea liquid and silicon sol solution are poured in the beaker of 2000ml; And mix; Hold the beaker of copper nitrate solution, urea liquid and silicon sol solution then respectively with the washed with de-ionized water of 50ml; Pour in the 2000ml beaker that fills copper nitrate, urea and Ludox mixed solution, use HNO
3The pH value of mixed solution is transferred to 2, with deionized water mixed solution is diluted to 1500ml then;
3), in being poured into, mixed solution adorns in the flask of 1～30kHz supersonic generator and agitator; And turn on agitator; Stir 60min; Solution is mixed; Heating then; And open supersonic generator solution is handled, keeping simultaneously stirring and finish up to reaction, reaction temperature is controlled at 95～100 ℃;
4), stirring reaction 24 hours, detect the pH value of solution with pH meter, reach at 6.8 ± 0.2 o'clock, the reaction end stops heating, stirring and ultrasonic Treatment;
5), will react the sediment washing accomplished 2～3 times, use absolute ethanol washing again 1～2 time with 50～60 ℃ of hot deionized waters;
6), the deposition that will wash after accomplishing changes in the drying box, dried deposition is broken, sieve at 120 ℃ of dry 12h down, the adding mass percent is 1～10 ‰ stearic acid in the sieve powder, mixes, compression molding again;
7), the product behind the compression molding is changed over to carry out roasting in the roaster; Temperature programming is adopted in roasting: initial temperature is 20 ℃; After 30 minutes, rise to 120 ℃ 120 ℃ of insulations 120 minutes, rose to 200 ℃ again through 60 minutes, rose to 300 ℃ again through 300 minutes 300 ℃ of insulations 120 minutes 200 ℃ of insulations 150 minutes; Rise to 450 ℃ again through 450 minutes 450 ℃ of insulations 300 minutes, change reduction furnace over to after coming out of the stove;
8), the flow velocity with per minute 100ml feeds hydrogen to reduction furnace; Temperature programmed reduction is 14 hours in the atmosphere of pure hydrogen; The temperature programmed reduction process is: initial temperature is 180 ℃, after 2 hours, rises to 220 ℃ 220 ℃ of insulations 14 hours, has both got the copper Si catalyst.
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|---|---|---|---|
| CN 201110266819 CN102380381B (en) | 2011-09-09 | 2011-09-09 | Nanometer ultrafine glycol copper silicon catalyst and preparation method thereof |
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|---|---|---|---|
| CN 201110266819 CN102380381B (en) | 2011-09-09 | 2011-09-09 | Nanometer ultrafine glycol copper silicon catalyst and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073399A (en) * | 2013-01-28 | 2013-05-01 | 爱斯特（成都）医药技术有限公司 | Preparation method of 3,5-dimethoxy phenylcarbinol |
| CN112844364A (en) * | 2021-02-07 | 2021-05-28 | 内蒙古久泰新材料有限公司 | Multi-metal catalyst and application thereof in preparation of lactide compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585890A (en) * | 1981-04-30 | 1986-04-29 | Ube Industries, Ltd. | Process for producing ethylene glycol and/or glycolic acid ester, catalyst composition used therefor, and process for production thereof |
| CN101757915A (en) * | 2010-01-08 | 2010-06-30 | 厦门大学 | Catalyst used for preparing glycol from hydrogenation of oxalates and preparation method 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 |
-
2011
- 2011-09-09 CN CN 201110266819 patent/CN102380381B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585890A (en) * | 1981-04-30 | 1986-04-29 | Ube Industries, Ltd. | Process for producing ethylene glycol and/or glycolic acid ester, catalyst composition used therefor, and process for production thereof |
| CN101757915A (en) * | 2010-01-08 | 2010-06-30 | 厦门大学 | Catalyst used for preparing glycol from hydrogenation of oxalates and preparation method 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 |
Non-Patent Citations (2)
| Title |
|---|
| LIANG-FENG CHEN ET AL: "Cu/SiO2 catalysts prepared by the ammonia-evaporation method: Texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol", 《JOURNAL OF CATALYSIS》 * |
| 李竹霞等: "载体对草酸二甲酯加氢铜基催化剂的影响", 《华东理工大学学报(自然科学版)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073399A (en) * | 2013-01-28 | 2013-05-01 | 爱斯特（成都）医药技术有限公司 | Preparation method of 3,5-dimethoxy phenylcarbinol |
| CN112844364A (en) * | 2021-02-07 | 2021-05-28 | 内蒙古久泰新材料有限公司 | Multi-metal catalyst and application thereof in preparation of lactide compound |
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|---|---|
| CN102380381B (en) | 2013-05-01 |
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Effective date of registration: 20191021 Address after: 017100 Erdos new road, Zhungeer Qi, the Inner Mongolia Autonomous Region Patentee after: Jiu Tai energy (Ordos) Co., Ltd. Address before: Luo jiulu 276017 Shandong province Linyi city Luozhuang District No. 203 Patentee before: Long Thai Energy Technology Co., Ltd. |
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