CN101559370A - Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof - Google Patents
Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof Download PDFInfo
- Publication number
- CN101559370A CN101559370A CNA2009100690434A CN200910069043A CN101559370A CN 101559370 A CN101559370 A CN 101559370A CN A2009100690434 A CNA2009100690434 A CN A2009100690434A CN 200910069043 A CN200910069043 A CN 200910069043A CN 101559370 A CN101559370 A CN 101559370A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ethyl acetate
- modified additive
- ethanol
- percent
- 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.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The method belongs to a Cu-Cr series ethyl acetate catalyst added with a modified additive and a manufacturing method thereof. The catalyst exists in the form of composite metal oxide, and components (according to the mass percentage which account for the total mass of the catalyst) are: 25 to 55 percent of Cu, 10 to 25 percent of Cr, 0 to 10 percent of Mg, 0 to 10 percent of Zr, and the balance of O, wherein the additives, namely the Mg and the Zr cannot be zero synchronously. A salt solution containing the Cu, the Cr, the Mg and the Zr which are evenly mixed is added with an alkaline precipitator under the condition of stirring according to the proportion, the pH value is controlled to be between 6 and 10 during the precipitation, and the aging time is between 0.2 and 20 hours; and the obtained precipitate is filtered and is washed by water until the filtrate is neutral. The precipitate is dried at a temperature of between 80 and 130 DEG C for 4 to 15 hours and then is roasted at a temperature of between 300 and 500 DEG C for 2 to 8hours to obtain a catalyst precursor. The catalyst has higher activity and selectivity than the prior catalyst.
Description
Technical field
This method belongs to the manufacture method that is used for specific synthetic chemistry catalysts, particularly adds the Cu-Cr series ethyl acetate catalyst and the manufacture method of modified additive.
Background technology
Ethyl acetate is a kind of organic solvent commonly used, is widely used in the production of products such as spices, medicine and diluent.As a kind of high-grade solvent, ethyl acetate will replace the various low-grade solvent of severe contamination air.According to authoritative institution's prediction, the whole world can reach 4.7% for the demand average growth rate per annum of ethyl acetate.
The method of industrial synthesizing ethyl acetate mainly contains four kinds: the one, and the catalytic esterification method of traditional acetate and ethanol; The 2nd, according to the acetaldehyde condensation method of Tischenko reaction, catalyst is an aluminium ethylate; The 3rd, ethene and acetate direct synthesis technique in the presence of heteropolyacid catalyst; The 4th, ethanol one step catalytic dehydrogenation method.
The raw material that ethanol with one-step method prepares ethyl acetate has only ethanol, because of ethanol can obtain from plant fermentation, needn't depend on non-renewable resources such as oil, it is a kind of Green Chemistry product that adapts to the sustainable development requirement, and the raw material of preparation ethanol can be regenerated, and makes with ethanol to be that the research of the various downstream product of feedstock production is causing people's attention gradually.From the angle of cost of investment, use ethanol to be the raw material ratio less expensive, nontoxic, pollution-free, be particularly suitable for combining with low-cost fermenting alcohol device.
The catalyst that Ethanol Method prepares ethyl acetate mainly contains Cu-Zn-Al and Cu-Cr diplobiont system, and the former does not see the industrialization report of success as yet, and the latter has set up the large-scale production of ethyl device of some cover tons all over the world.
Although Cu-Zn-Al series catalysts conversion ratio is higher, but exist following point: the one, selectivity is not high enough, the selectivity of ethyl acetate is lower than 93%, mentions as article Journal of Catalysis 212 (2002) 207-215 and Chinese patent CN1062304A; The 2nd, contain more butanone in the accessory substance, butanone and ethyl acetate can form azeotropic mixture, have had a strong impact on the purification refine process of product.
Though existing C u-Cr series catalysts has higher selectivity, reach 95～98%, it is lower but to exist catalyst conversion per pass activity, has only 30～35%, causes the production cost of ethyl acetate higher.Patent CN1644239 has proposed to improve the performance of Cu-Cr catalyst with Ag as auxiliary agent, and activity is improved, but the ethyl acetate selectivity is lower, is about 90%.
Summary of the invention
The object of the invention is to provide a kind of novel high-performance Cu-Cr series ethyl acetate catalyst and manufacture method of adding modified additive, and this catalyst is an auxiliary agent with metal oxides such as Mg, Zr, has activity and the selectivity higher than existing catalyst.
The Cu-Cr series ethyl acetate catalyst of interpolation modified additive of the present invention, the form of catalyst composite metal oxide exists, and it is as follows that each component accounts for the quality percentage composition of catalyst gross mass:
Cu 25～55％，
Cr 10～25％，
Mg 0～10％，
Zr 0～10％，
Surplus is an oxygen.
Wherein auxiliary agent Mg, Zr can not be 0 simultaneously.
The manufacture method of catalyst of the present invention will contain the mixed uniformly salting liquid of Cu, Cr, Mg and Zr in proportion and add alkaline precipitating agent under the state that stirs, and precipitation process pH value is controlled at 6～10, and ageing time is 0.2～20h; Sedimentation and filtration, the water that obtains cleaned to filtrate be neutral.Behind 80～130 ℃ of drying 4～15h,, obtain the catalyst precursor at 300～500 ℃ of following roasting 2～8h.
Auxiliary agent Mg and Zr also can utilize equi-volume impregnating to add in the Cu-Cr catalyst, and auxiliary agent adds simultaneously with any or both of the soluble-salt of Mg, Zr, converts corresponding oxide after roasting to.
Catalyst activation process adopts usual way to get final product, and for activating at 250 ℃ of following low-temperature reductions, activation phenomenon is 10% H
2-90%N
2Mixed airflow, recovery time 3h.
The activity of such catalysts evaluation is carried out in fixed-bed micro-devices, and reactor is made by the stainless steel tube of long 300mm, internal diameter 8mm, and loaded catalyst is 1mL (20～40 order).Before activity rating began, catalyst need reduce, and after reduction finished, feed ethanol was pumped into the preheater vaporization by the high pressure micro-measurement, and the ethanol after the vaporization enters in the reactor and reacts, and product is analyzed by gas-chromatography.
The specific embodiment
Comparative example 1:Cu-Cr-O Preparation of Catalyst
With 19.2 gram Cu (NO
3)
26H
2O and 25.9 gram Cr (NO
3)
39H
2O (the Cu/Cr mol ratio is 1: 1) makes even mixing salt solution, with concentration be the sodium hydroxide solution of 0.5N under stirring and stream join in the reactor, hierarchy of control pH value is 8, after precipitation finished, aging 5h filtered, water washing is to filtering and being neutral, at 110 ℃ of dry 5h, 400 ℃ of roasting 2h promptly make precursor.With precursor at 10%H
2-90%N
2Behind 250 ℃ of following in-situ reducing 3h, promptly make fresh Cu-Cr-O catalyst in the mixed airflow.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh catalyst, and the liquid volume air speed is 0.6h
-1, reaction temperature is 220 ℃, and recording ethanol conversion is 30%, and ethyl acetate selectivity 80%, acetaldehyde selectivity are 13%.
Comparative example 2:Cu-Cr-O Preparation of Catalyst
The preparation method is with comparative example 1, but Cu: Cr:=0.5 in this example: 1 (mol ratio), precipitating reagent are the aqueous sodium carbonate of 0.75N, and the PH of control solution is 7.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh Cu-Cr-O catalyst, and the liquid volume air speed is 0.6h
-1, reaction temperature is 220 ℃, and recording ethanol conversion is 25%, and ethyl acetate selectivity 70%, acetaldehyde selectivity are 15%.
Comparative example 3:Cu-Cr-O Preparation of Catalyst
With comparative example 1, but Cu: Cr:=2 in this example: 1 (mol ratio), precipitating reagent are 1N ammoniacal liquor, and the PH of control solution is 10, and the catalyst roasting condition is 300 ℃ of 10h.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh Cu-Cr-O catalyst, and the liquid volume air speed is 0.6h
-1, reaction temperature is 220 ℃, and recording ethanol conversion is 36%, and ethyl acetate selectivity 74%, acetaldehyde selectivity are 11%.
Embodiment 1:Cu-Cr-Mg-O Preparation of Catalyst
With 20 gram Mg (NO
3)
26H
2O is dissolved in the distilled water, loads on by 15 of the preparation of the method in the comparative example 2 according to equi-volume impregnating to restrain on the Cu-Cr-O catalyst precursors, through 450 ℃ of roasting 4h, promptly obtains the catalyst precursor.This precursor is at 10%H
2-90%N
2In the mixed airflow, promptly make fresh Cu-Cr-Mg-O catalyst behind the process in-situ reducing 3h down at 250 ℃.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh Cu-Cr-Mg-O catalyst, and the liquid volume air speed is 0.6h
-1, reaction temperature is 230 ℃, and recording ethanol conversion is 48%, and ethyl acetate selectivity 94%, acetaldehyde selectivity are 2%.
Embodiment 2:Cu-Cr-Zr-O Preparation of Catalyst
With 6 gram ZrOCl
28H
2O is dissolved in the distilled water, loads on by 15 of the preparation of the method in the comparative example 3 according to equi-volume impregnating to restrain on the Cu-Cr-O catalyst precursors.Through 400 ℃ of roasting 8h, promptly obtain the catalyst precursor.This precursor is at 10%H
2-90%N
2In the mixed airflow, promptly make fresh Cu-Cr-Zr-O catalyst behind the process in-situ reducing 3h down at 250 ℃.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh Cu-Cr-Zr-O catalyst, and the liquid volume air speed is 0.6h
-1, reaction temperature is 230 ℃, and recording ethanol conversion is 43%, and ethyl acetate selectivity 90%, acetaldehyde selectivity are 3%.
Embodiment 3:Cu-Cr-Mg-Zr-O Preparation of Catalyst
With 3 gram ZrOCl
28H
2O and 10 gram Mg (NO
3)
26H
2O is dissolved in the distilled water, loads on by 15 of the preparation of the method in the comparative example 1 according to equi-volume impregnating to restrain on the catalyst precursors.Through 400 ℃ of roasting 2h, promptly obtain the catalyst precursor.This precursor is at 10%H
2-90%N
2Promptly obtain fresh Cu-Cr-Mg-Zr-O catalyst behind the process in-situ reducing 3h down at 250 ℃ in the mixed airflow.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh Cu-Cr-Mg-Zr-O catalyst, and the liquid volume air speed is 0.5h
-1, reaction temperature is 220 ℃, and recording ethanol conversion is 45%, and ethyl acetate selectivity 96%, acetaldehyde selectivity are 2%.
Embodiment 4:Cu-Cr-Mg-O Preparation of Catalyst
With 19.2 gram Cu (NO
3)
26H
2O and 25.9 gram Cr (NO
3)
39H
2O and 2 gram Mg (NO
3)
26H
2O is dissolved in and makes even mixing salt solution in the distilled water, under agitation the 1N sodium hydroxide solution is also flowed simultaneously to add in the reactor, and control PH is 6, after precipitation finished, aging 10h, was filtered to filtrate and is neutral water washing, filter cake is at 130 ℃ of dry 4h, and 300 ℃ of roasting 10h promptly make precursor.This precursor is at 10%H
2-90%N
2In the mixed airflow, promptly make fresh Cu-Cr-Mg-O catalyst behind the process in-situ reducing 3h down at 250 ℃.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh Cu-Cr-Mg-O catalyst, and the liquid volume air speed is 0.6h
-1, reaction temperature is 220 ℃, and recording ethanol conversion is 50%, and ethyl acetate selectivity 90%, acetaldehyde selectivity are 3%.
Embodiment 5:Cu-Cr-Mg-O Preparation of Catalyst
With 19.2 gram Cu (NO
3)
26H
2O and 25.9 gram Cr (NO
3)
39H
2O and 7 gram Mg (NO
3)
26H
2O is dissolved in and makes even mixing salt solution in the distilled water, under agitation the 1N sodium hydroxide solution is also flowed simultaneously to add in the reactor, and control PH is 7, after precipitation finished, aging 20h, was filtered to filtrate and is neutral water washing, filter cake is at 80 ℃ of dry 15h, and 400 ℃ of roasting 6h promptly make precursor.This precursor is at 10%H
2-90%N
2In the mixed airflow, promptly make fresh Cu-Cr-Mg-O catalyst behind the process in-situ reducing 3h down at 250 ℃.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh Cu-Cr-Mg-O catalyst, and the liquid volume air speed is 0.6h
-1, reaction temperature is 220 ℃, and recording ethanol conversion is 49%, and ethyl acetate selectivity 92%, acetaldehyde selectivity are 3%.
Embodiment 6:Cu-Cr-Zr-O Preparation of Catalyst
With 19.2 gram Cu (NO
3)
26H
2O and 25.9 gram Cr (NO
3)
39H
2O and and 0.5 gram ZrOCl
28H
2O is dissolved in the distilled water, makes even mixing salt solution, under agitation with 1N Na
2CO
3-NaOH mixed ammonium/alkali solutions also flows simultaneously and adds in the reactor, and hierarchy of control pH value is 7, and all the other subsequent preparation methods promptly make fresh Cu-Cr-Zr-O catalyst with comparative example 1.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh Cu-Cr-Zr-O catalyst, and the liquid volume air speed is 0.6h
-1, reaction temperature is 220 ℃, and recording ethanol conversion is 47%, and ethyl acetate selectivity 85%, acetaldehyde selectivity are 3%.
Embodiment 7:Cu-Cr-Zr-O Preparation of Catalyst
With 19.2 gram Cu (NO
3)
26H
2O and 25.9 gram Cr (NO
3)
39H
2O and and 1.5 gram ZrOCl
28H
2O is dissolved in the distilled water, makes even mixing salt solution, under agitation with 0.75N Na
2CO
3-NaOH mixed ammonium/alkali solutions also flows simultaneously and adds in the reactor, and hierarchy of control pH value is 10, aging 0.2h, and 600 ℃ of all the other subsequent preparation methods of roasting 6h promptly make fresh Cu-Cr-Zr-O catalyst with comparative example 1.
The continuous feeding of ethanol is equipped with in the tubular reactor of fresh Cu-Cr-Zr-O catalyst, and the liquid volume air speed is 0.6h
-1, reaction temperature is 220 ℃, and recording ethanol conversion is 47%, and ethyl acetate selectivity 82%, acetaldehyde selectivity are 3%.
Claims (3)
1. it is as follows that Cu-Cr series ethyl acetate catalyst that adds modified additive, each component account for the quality percentage composition of catalyst gross mass:
Cu 25～55％，
Cr 10～25％，
Mg 0～10％，
Zr 0～10％，
Surplus is an oxygen.
Wherein auxiliary agent Mg, Zr can not be 0 simultaneously.
2. the manufacture method of the Cu-Cr series ethyl acetate catalyst of the interpolation modified additive of claim 1, it is characterized in that to contain in proportion the mixed uniformly salting liquid of Cu, Cr, Mg and Zr and under the state that stirs, add alkaline precipitating agent, precipitation process pH value is controlled at 6～10, and ageing time is 0.2～20h; Sedimentation and filtration, the water that obtains cleaned to filtrate be neutral.Behind 80～130 ℃ of drying 4～15h,, obtain the catalyst precursor at 300～600 ℃ of following roasting 2～10h.
3. the manufacture method of the Cu-Cr series ethyl acetate catalyst of the interpolation modified additive of claim 1, it is characterized in that auxiliary agent Mg and Z utilize equi-volume impregnating to add in the Cu-Cr catalyst, auxiliary agent adds simultaneously with any or both of the soluble-salt of Mg, Zr, converts corresponding oxide after roasting to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100690434A CN101559370A (en) | 2009-05-27 | 2009-05-27 | Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100690434A CN101559370A (en) | 2009-05-27 | 2009-05-27 | Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101559370A true CN101559370A (en) | 2009-10-21 |
Family
ID=41218449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100690434A Pending CN101559370A (en) | 2009-05-27 | 2009-05-27 | Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101559370A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880662A (en) * | 2014-03-12 | 2014-06-25 | 江苏大学 | Preparation method for preparing ethyl acetate by directly dehydrogenizing ethanol |
| CN104646058A (en) * | 2015-02-09 | 2015-05-27 | 山东师范大学 | Copper-containing complex catalyst and preparation method and application thereof |
| CN112206820A (en) * | 2020-09-30 | 2021-01-12 | 润泰化学（泰兴）有限公司 | Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof |
-
2009
- 2009-05-27 CN CNA2009100690434A patent/CN101559370A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880662A (en) * | 2014-03-12 | 2014-06-25 | 江苏大学 | Preparation method for preparing ethyl acetate by directly dehydrogenizing ethanol |
| CN103880662B (en) * | 2014-03-12 | 2016-08-24 | 江苏大学 | A kind of ethanol direct dehydrogenation prepares the preparation method of ethyl acetate |
| CN104646058A (en) * | 2015-02-09 | 2015-05-27 | 山东师范大学 | Copper-containing complex catalyst and preparation method and application thereof |
| CN112206820A (en) * | 2020-09-30 | 2021-01-12 | 润泰化学（泰兴）有限公司 | Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof |
| CN112206820B (en) * | 2020-09-30 | 2022-11-22 | 润泰化学（泰兴）有限公司 | Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617518B (en) | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation | |
| CN102320970B (en) | Method for preparing tributyl citrate by using modified cation exchange resin as catalyst | |
| CN104624196B (en) | A kind of high-specific surface area fischer-tropsch synthetic catalyst and preparation method and application | |
| CN102304045B (en) | Integrated process for synthesizing acetyl tributyl citrate (ATBC) from active carbon solid-carried sulphuric acid catalyst | |
| CN103372453A (en) | Catalyst for synthesis of methyl glycolate and preparation method thereof | |
| CN102179245B (en) | Application of palladium/active carbon catalyst in synthesizing N,N'-dibenzylethylenediamine | |
| CN101768168B (en) | Method for synthesizing cephalosporin intermediate | |
| CN103100393A (en) | Hydrogenation catalyst and preparation method thereof | |
| CN101559370A (en) | Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof | |
| CN102875332B (en) | Process for synthesizing 3-hexyne-2,5-diol through slurry bed based on low pressure method | |
| CN101811042A (en) | Selective hydrogenation catalyst and preparation method and application thereof | |
| CN102476056A (en) | Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof | |
| CN103316696A (en) | Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method | |
| CN101565389A (en) | Method for catalyzing and synthesizing hexamethylene-1,6-diamino methyl formate by using oxide | |
| CN110105173A (en) | A kind of purification process of efficient HPPO technique recycling design | |
| CN102258994B (en) | Method for preparing catalyst used in synthesizing isophorone through acetone multiphase method | |
| CN1962636A (en) | 2,Process for preparing 3-dimethylpyridine | |
| CN100453178C (en) | Catalyst for synthesizing iso-propylbenzene | |
| CN102344378B (en) | Amino alcohol preparation method using aqueous amino acid | |
| CN110054547A (en) | A method of using integrated catalyst coupling and catalyzing preparing ethanol by oxalate hydrogenation | |
| CN105152938B (en) | A kind of technique efficiently synthesizing secondary carbon primary amine N1923 | |
| CN113582860B (en) | Preparation method of N-methyl monoethanolamine | |
| CN104557707A (en) | Caprolactam hydrofining method | |
| CN109096049A (en) | A kind of method that esterification eliminates dimethyl ester mesoxalic acid and obtains polyester grade ethylene glycol | |
| CN115322117B (en) | Preparation process of high-purity methacrylonitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20091021 |