CN103949252A - Catalyst for direct preparation of acetonitrile from ethanol and preparation method thereof - Google Patents
Catalyst for direct preparation of acetonitrile from ethanol and preparation method thereof Download PDFInfo
- Publication number
- CN103949252A CN103949252A CN201410141830.6A CN201410141830A CN103949252A CN 103949252 A CN103949252 A CN 103949252A CN 201410141830 A CN201410141830 A CN 201410141830A CN 103949252 A CN103949252 A CN 103949252A
- Authority
- CN
- China
- Prior art keywords
- cuo
- preparation
- catalyst
- acetonitrile
- ethanol
- 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
Abstract
The invention relates to a catalyst for direct preparation of acetonitrile from ethanol and a preparation method thereof, and mainly solves the problems of low catalytic activity, low product selectivity and poor catalyst stability in the prior art. The catalyst adopts copper oxide CuO as a main body, and alumina, zirconium dioxide, nickel oxide or zinc oxide are mixed with CuO to form the catalyst; the catalyst well solves the above problems, and can be used in acetonitrile industrial production.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, be specifically related to the Catalysts and its preparation method that ethanol is directly prepared acetonitrile.
Background technology
Acetonitrile is the frequent extractant as isoprene, butadiene cut in petrochemical industry; Be raw material or the intermediate of important agricultural chemicals, medicine, dyestuff and synthetic perfume, be also used as analytical reagent and carry out efficient liquid phase chromatographic analysis simultaneously.From the data of having delivered, alcohol dehydrogenase ammonification synthesizing acetonitrile raw material availability added value high, byproduct is high, has become the focus of current research, by the reaction of ethanol ammonification synthesizing acetonitrile, is:
C2H5OH+NH3 CH3CN+2H2+H2O
There is in early days in the world patent research: as catalyst, carrier can be silica, diatomite, silica gel, float stone or alum clay etc., the best results of silica gel in several carriers with phosphato-molybdic heteropolyacid H3PMo12O4.The bulk density of take is made carrier as 0.75g/cm3, specific area are about 500m2/g silica gel, and is wrapped painting with the 12-molybdophosphate of 10-35%.Suitable process conditions (reaction temperature is 380 ~ 420 ℃, and the mol ratio of ethanol and ammonia is 1:(3 ~ 4), the time of staying is 5s, under normal pressure) to evaluate, ethanol conversion reaches with acetonitrile and is selectively respectively 96% and 65%.
In people's reported first such as Roger of U.S. Cyanamid company in 1981 can catalysis ethanol synthesizing acetonitrile with 15%Cu/Al2O3 and 5%Cu5%Zn/Al2O3, under optimum reaction condition, the yield of acetonitrile is up to 87%.
Domestic Tsing-Hua University by selecting Zn, Al, La and Ce oxide to improve the catalytic activity at Cu center as carrier, is to obtain good reaction result under the condition of 315 ℃ in reaction temperature in 1992 disclosed patent [54].
The Feng Cheng of Hebei University of Technology etc. utilize co-precipitation-kneading legal system standby the reaction for alcohol dehydrogenase ammonification synthesizing acetonitrile of novel Co-Ni/ γ-Al2O3 catalyst, under the condition that is 100% at ethanol conversion, the yield of acetonitrile has reached 92.6%.This catalyst is with they compare [56] by this type of catalyst of research before, and mechanical strength has had obvious improvement, but this reaction condition is harsher, and reaction temperature is that 420 ℃, reactant liquefied ammonia consumption are very large.
But above-mentioned document and patent all exist catalyst activity, selective, stability and reaction condition problem preferably simultaneously, them have been limited in the prospect of commercial Application.
Summary of the invention
Technical problem to be solved by this invention is low, the selective problem of low, less stable and required severe reaction conditions of catalyst activity in conventional art, and a kind of new catalyst of preparing acetonitrile for ethanol is provided.It is high that this catalyst has conversion ratio, selectively good, good stability, the feature of required reaction condition gentleness.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: several catalyst of preparing acetonitrile for ethanol, by weight percentage, comprise following component:
1, CuO/Al
2o
3system:
1a) the CuO of 5-60%;
1b) the Al of 95-40%
2o
3;
In technique scheme, the consumption preferable range of CuO is 10-40% by weight percentage, and the consumption of CuO more preferably scope is 15-35%.
2, CuO/ZnO/Al
2o
3system:
2a) the CuO of 5-40%;
2b) the ZnO of 1-50%;
2c) the Al of 94-10%
2o
3;
In technique scheme, the consumption preferable range of CuO is 10-30% by weight percentage, and the consumption preferable range of ZnO is 2.5-40%; The consumption of CuO more preferably scope is 15-30%, and the consumption preferable range of ZnO is 12-20%;
3, CuO/ZrO
2system:
3a) the CuO of 3-40%;
3b) the ZrO of 97-60%
2;
In technique scheme, the consumption preferable range of CuO is 3-30% by weight percentage, and the consumption of CuO more preferably scope is 5-20%.
4, CuO/NiO/ZrO
2system:
4a) the CuO of 3-30%;
4b) the NiO of 6-60%;
4c) the ZrO of 91-10%
2;
In technique scheme, the consumption preferable range of CuO is 5-30% by weight percentage; NiO's
Consumption preferable range is 10-60%; It is 5-17% that the consumption of CuO more selects scope; The consumption of NiO more preferably scope is 15-51%;
Carrier of the present invention is chamber preparation or purchase shaping carrier by experiment, in carrier preparation process, can add boiling to process, the preparation method of catalyst can adopt dipping, the precipitation method, evenly co-precipitation, physical mixed, the method preparations such as urea coprecipitation, preferred method, for dipping and even coprecipitation, is then dried, moulding, roasting.
Catalyst of the present invention has the selective of very high activity and nearly 100%, and has fabulous stability, and the raw material of this catalyst is easy to get, and is easy to sit on repeatability preparation in preparation method, is convenient to industrial-scale production.
Catalyst prepared by the present invention is in ethanol ammonification synthesizing acetonitrile process route, and reaction condition is: normal pressure, and reaction temperature 250-300 ℃, the mol ratio of ethanol and ammonia is 1:1-7, the weight (hourly) space velocity (WHSV) of ethanol is 0.25-2h
-1, reactor is continuous fixed bed reactor.The conversion ratio of this catalyst ethanol can reach 99%, selectively can the reaching more than 99% of acetonitrile.
The specific embodiment
The substantial feature that the present invention gives prominence to can be embodied from following embodiment, but they are not that the present invention is done to any restriction.
Embodiment 1:
Measuring quality is 4.52 gCu (NO
3)
2 .3H
2o is dissolved in 20.0 g deionized waters and is mixed with certain density solution, measures 6g γ-Al simultaneously
2o
3put into container, the solution of preparation is poured in this container and stirred, after waiting to stir, be put in 45 ℃ of baking ovens and be dried 11 hours to Powdered, proceed in Muffle furnace at 500 ℃ roasting 3 hours, the catalyst granules that the catalyst fines after roasting obtains between granule size 20 ~ 40 orders through compressing tablet, after pulverizing, sieving is standby.
Catalytic reaction condition: this reaction adopts continuous flow reactor of fixed bed.
Reducing gases: 5%H
2/ 95%N
2gaseous mixture
Reduction temperature: 235 ℃
Reaction temperature: 290 ℃
The weight (hourly) space velocity (WHSV) 1.2h of ethanol
-1
Ethanol/NH
3(mol) 1/6
Reaction result is in Table 1.
Embodiment 2:
The deionized water that adds 200ml in stirred vessel, by the sodium bicarbonate aqueous solution of 1M and 4.54gCu (NO
3)
2 .3H
2o and 44gAl (NO
3)
3 .9H
2the mixed liquor of O splashes in stirred vessel jointly, homogeneous precipitation, in precipitation process, keep PH 8.0, temperature remains on 80 ℃, after precipitation is complete, static aging 2 hours, filter resulting suspension and wash until the electrical conductivity of filtrate is approximately 20 μ S by deionized water, after having washed, filter cake is put into drying box dry 11h at 120 ℃, after being dried completely, proceed to Muffle furnace roasting catalyst granules that after 12 hours, compression molding obtains between granule size 20 ~ 40 orders at 400 ℃ standby, catalytic reaction condition is with embodiment 1, and reaction result is in Table 1.
Embodiment 3:
The deionized water that adds 200ml in stirred vessel, by the sodium bicarbonate aqueous solution of 1M and 4.54gCu (NO
3)
2 .3H
2o, 5.58gZn (NO
3)
2 .6H
2o and 44gAl (NO
3)
3 .9H
2the mixed liquor of O splashes in stirred vessel jointly, homogeneous precipitation, in precipitation process, keep PH 8.0, temperature remains on 80 ℃, after precipitation is complete, and static aging 2 hours, filter resulting suspension and wash until the electrical conductivity of filtrate is approximately 20 μ s by deionized water, after having washed, filter cake is put into drying box dry 11h at 120 ℃, dry to proceed to Muffle furnace roasting catalyst granules that after 12 hours, compression molding obtains between granule size 20 ~ 40 orders at 400 ℃ after completely standby.Catalytic reaction condition is with embodiment 1, and reaction result is in Table 1.
Embodiment 4:
In stirred vessel, add a certain amount of deionized water, by 20% aqueous sodium carbonate and 6.81gCu (NO
3)
2 .3H
2o and 15.71gZrOCl
2 .8H
2the mixed liquor of O splashes in stirred vessel jointly, homogeneous precipitation, in precipitation process, keep PH 7.0, temperature remains on 70 ℃, after precipitation is complete, static aging 2 hours, filter resulting suspension and wash until the electrical conductivity of filtrate is approximately 20 μ S by deionized water, after having washed, filter cake being put into drying box dry at 150 ℃, dry proceed to Muffle furnace roasting 4 hours at 500 ℃ after completely, the catalyst granules that compression molding obtains between granule size 20 ~ 40 orders is standby.Catalytic reaction condition except reduction temperature be 280 ℃, other are with embodiment 1, reaction result is in Table 1.
Embodiment 5:
Take the ZrOCl of 50g
2 .8H
2o is dissolved in 1000ml deionized water, this solution is dropwise splashed in 25% ammoniacal liquor, until the PH of titration end-point is 10, finishes titration, and whole process is about 1 hour, and the consumption of ammoniacal liquor is 200ml.The zirconium hydroxide sols ageing that precipitation is obtained, washing are removed after Cl ion, and dry 8h at 90 ℃, puts into Muffle furnace roasting 3h at 450 ℃ afterwards, can obtain required ZrO
2.Measure the Cu (NO of 2.27g
3)
2 .3H
2o is dissolved in the solution that is mixed with desired concn in the deionized water of 10ml, puts into afterwards 6g carrier ZrO in crucible
2the copper nitrate solution preparing is poured in crucible and is stirred to evenly, in drying box, at 45 ℃, be dried to afterwards Powdered, proceed to again in Muffle furnace at 500 ℃ roasting 3 hours, catalyst fines after roasting is after compressing tablet, pulverizing, after 20 ~ 40 mesh sieve screenings, obtain the solid that granule size is suitable, be required Catalysts Cu/ZrO
2.Catalytic reaction condition is with embodiment 4, and reaction result is in Table 1.
Embodiment 6:
Take the ZrOCl of 50g
2 .8H
2o is dissolved in 1000ml deionized water, this solution is dropwise splashed in 25% ammoniacal liquor, until the PH of titration end-point is 10, finishes titration, and whole process is about 1 hour, and the consumption of ammoniacal liquor is 200ml.The zirconium hydroxide sols that precipitation is obtained seals together with mother liquor, at a certain temperature boiling; Boiling certain hour is afterwards by sedimentation and filtration, till not measuring Cl ion with distilled water cyclic washing to inspection; By filter cake dry 8h at 90 ℃, put into afterwards Muffle furnace roasting 3h at 450 ℃, can obtain required ZrO
2.Measure the Cu (NO of 1.14g
3)
2 .3H
2o is dissolved in 10ml deionized water, puts into afterwards 6g carrier ZrO in crucible
2the copper nitrate solution preparing is poured in crucible and is stirred to evenly, in drying box, at 45 ℃, be dried to afterwards Powdered, proceed to again in Muffle furnace at 500 ℃ roasting 3 hours, catalyst fines after roasting is after compressing tablet, pulverizing, after 20 ~ 40 mesh sieve screenings, obtain the solid that granule size is suitable, be required Catalysts Cu/ZrO
2.Catalytic reaction condition is with embodiment 4, and reaction result is in Table 1.
Embodiment 7:
By 20% aqueous sodium carbonate and weight fraction, be that 4.48 %Ni(are in NiO), 1.52 %Cu(are in CuO) and 2.82 %Zr(with ZrO
2the mixed aqueous solution of nickel nitrate, copper nitrate and zirconium oxychloride meter) precipitates in stirred vessel with constant material stream simultaneously, and keeping pH is 7.0, and precipitation temperature is 70 ℃.After Cl ion is removed in the suspension washing that precipitation is obtained, in drying box at the temperature of 150 ℃ dry cake.Subsequently at the temperature of 450-500 ℃ to hydroxide-carbonate mixture roasting of obtaining 4 hours.Catalyst fines after roasting, after compressing tablet, pulverizing, obtains after 20 ~ 40 mesh sieves screenings the solid that granule size is suitable, and so the catalyst weight mark of preparation is composed as follows: 51%NiO, 17%CuO, 32%ZrO
2.Catalytic reaction condition is with embodiment 4, and reaction result is in Table 1.
Table 1.
Claims (8)
1. ethanol is directly prepared a Catalysts and its preparation method for acetonitrile, it is characterized in that it is that to take cupric oxide and zirconium dioxide or cupric oxide and aluminium oxide be main body, sneaks into other component and forms, and said other components are zinc oxide, nickel oxide; By weight percentage, comprise following component:
CuO/Al
2o
3system:
1a) the CuO of 5-60%;
1b) the Al of 95-40%
2o
3.
2. ethanol according to claim 1 is directly prepared the Catalysts and its preparation method of acetonitrile, it is characterized in that the consumption of CuO is 15-40% by weight percentage.
3. ethanol according to claim 1 is directly prepared the Catalysts and its preparation method of acetonitrile, it is characterized in that measuring by weight percentage:
CuO/ZnO/Al
2o
3system:
2a) the CuO of 5-40%;
2b) the ZnO of 1-50%;
2c) the Al of 94-10%
2o
3.
4. ethanol according to claim 3 is directly prepared the Catalysts and its preparation method of acetonitrile, it is characterized in that the consumption of CuO is 15-30% by weight percentage, and the consumption of ZnO is 10-30%.
5. ethanol according to claim 1 is directly prepared the Catalysts and its preparation method of acetonitrile, it is characterized in that measuring by weight percentage:
CuO/ZrO
2system:
3a) the CuO of 3-40%;
3b) the ZrO of 97-60%
2.
6. ethanol according to claim 5 is directly prepared the Catalysts and its preparation method of acetonitrile, it is characterized in that the consumption of CuO is 5-25% by weight percentage.
7. ethanol according to claim 1 is directly prepared the Catalysts and its preparation method of acetonitrile, it is characterized in that measuring by weight percentage:
CuO/NiO/ZrO
2system:
4a) the CuO of 3-30%;
4b) the NiO of 6-60%;
4c) the ZrO of 91-10%
2.
8. the preparation method of the said catalyst of claim 7, is characterized in that the consumption of CuO is 5-20% by weight percentage; The consumption of NiO is 20-51%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410141830.6A CN103949252A (en) | 2014-04-10 | 2014-04-10 | Catalyst for direct preparation of acetonitrile from ethanol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410141830.6A CN103949252A (en) | 2014-04-10 | 2014-04-10 | Catalyst for direct preparation of acetonitrile from ethanol and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103949252A true CN103949252A (en) | 2014-07-30 |
Family
ID=51326678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410141830.6A Pending CN103949252A (en) | 2014-04-10 | 2014-04-10 | Catalyst for direct preparation of acetonitrile from ethanol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103949252A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104984751A (en) * | 2015-06-15 | 2015-10-21 | 广西新晶科技有限公司 | Metallic oxide catalyst and preparation method thereof |
| CN107876085A (en) * | 2017-11-15 | 2018-04-06 | 昌邑市瑞海生物科技有限公司 | A kind of preparation method of the special-purpose catalyst of synthesizing acetonitrile |
| CN109999903A (en) * | 2019-04-26 | 2019-07-12 | 中触媒新材料股份有限公司 | A kind of catalyst and preparation method thereof synthesizing acetonitrile |
| CN110302834A (en) * | 2019-06-28 | 2019-10-08 | 苏州仕净环保科技股份有限公司 | A kind of method for preparing catalyst and catalyst administered for nitrogen oxides |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015788A (en) * | 1989-04-27 | 1991-05-14 | Basf Aktiengesellschaft | Process for the hydrogenation of acetylenic alcohols |
| CN1062303A (en) * | 1992-01-31 | 1992-07-01 | 清华大学 | Be used for catalyzer by ethanol and ammonia synthesis acetonitrile |
| CN101602691A (en) * | 2009-07-16 | 2009-12-16 | 北京智博凯源科技有限公司 | Method by alcohol and/or aldehyde ammonia fluidized dehydrogenation one-step synthetising nitrile |
| JP2013184908A (en) * | 2012-03-06 | 2013-09-19 | Shimane Prefecture | Method for producing useful compound from acetonitrile |
-
2014
- 2014-04-10 CN CN201410141830.6A patent/CN103949252A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015788A (en) * | 1989-04-27 | 1991-05-14 | Basf Aktiengesellschaft | Process for the hydrogenation of acetylenic alcohols |
| CN1062303A (en) * | 1992-01-31 | 1992-07-01 | 清华大学 | Be used for catalyzer by ethanol and ammonia synthesis acetonitrile |
| CN101602691A (en) * | 2009-07-16 | 2009-12-16 | 北京智博凯源科技有限公司 | Method by alcohol and/or aldehyde ammonia fluidized dehydrogenation one-step synthetising nitrile |
| JP2013184908A (en) * | 2012-03-06 | 2013-09-19 | Shimane Prefecture | Method for producing useful compound from acetonitrile |
Non-Patent Citations (1)
| Title |
|---|
| 李俊飞: ""乙醇氨化合成乙腈Cu系催化剂改性及稳定性的研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 3, 15 March 2013 (2013-03-15) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104984751A (en) * | 2015-06-15 | 2015-10-21 | 广西新晶科技有限公司 | Metallic oxide catalyst and preparation method thereof |
| CN104984751B (en) * | 2015-06-15 | 2018-08-24 | 广西新晶科技有限公司 | A kind of metal oxide catalyst and preparation method thereof |
| CN107876085A (en) * | 2017-11-15 | 2018-04-06 | 昌邑市瑞海生物科技有限公司 | A kind of preparation method of the special-purpose catalyst of synthesizing acetonitrile |
| CN109999903A (en) * | 2019-04-26 | 2019-07-12 | 中触媒新材料股份有限公司 | A kind of catalyst and preparation method thereof synthesizing acetonitrile |
| CN110302834A (en) * | 2019-06-28 | 2019-10-08 | 苏州仕净环保科技股份有限公司 | A kind of method for preparing catalyst and catalyst administered for nitrogen oxides |
| CN110302834B (en) * | 2019-06-28 | 2022-07-01 | 苏州仕净科技股份有限公司 | Preparation method of catalyst for nitrogen oxide treatment and catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107285334B (en) | A kind of method and catalyst of synthesis in solid state AEI type molecular sieve | |
| US20150165432A1 (en) | Catalysts for preparation of butadiene by oxydehydrogenation of butene in fluidized bed reactor and method of preparing same and use of same | |
| CN102302934B (en) | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst | |
| CN103949252A (en) | Catalyst for direct preparation of acetonitrile from ethanol and preparation method thereof | |
| CN102755897A (en) | Method for preparing catalyst for methanol dehydrogenation to methyl formate through step coprecipitation-spray process | |
| CN101486479B (en) | Method for simply synthesizing gamma-Al2O3 and use thereof in ethanol dehydration | |
| CN103480377A (en) | Preparation method of copper based catalyst for methanol synthesis | |
| CN103691432A (en) | Ruthenium/aluminum oxide catalyst, as well as preparing method and application thereof | |
| CN103657658A (en) | Carboxylic ester hydrogenation catalyst and method for preparing cyclohexanol and ethanol | |
| CN103539635B (en) | Method for preparing isopropyl alcohol by acetone hydrogenation | |
| WO2021109611A1 (en) | Catalyst for hydrogenolysis and preparation method therefor | |
| CN102728361A (en) | Catalyst for isopropyl alcohol preparation through acetone hydrogenation and application thereof | |
| CN111229228A (en) | CO (carbon monoxide)2Complete methanation catalyst and preparation and application thereof | |
| CN104815662A (en) | Low-temperature high-activity nano-composite catalyst for methanation of synthesis gas and preparation method thereof | |
| CN113101968A (en) | Catalyst and method for preparing glycine methyl ester and glycine by catalyzing and aminating methyl glycolate | |
| CN106890669B (en) | A kind of catalyst producing methyl acetate, preparation method and application | |
| CN109422638B (en) | Method for preparing ketone compound by ABE fermentation liquor conversion | |
| CN111054326A (en) | Supported catalyst, preparation method thereof and application of supported catalyst in catalyzing synthesis of indole from ethylene glycol and aniline | |
| CN106311321A (en) | Catalyst containing EU-1/ZSM-5 eutectic zeolite as well as preparation method and application thereof | |
| CN106513001B (en) | It is a kind of by the catalyst and preparation method of synthesis gas synthesizing alcohol and application | |
| US20070149818A1 (en) | Process for producing nitrogen-containing compounds | |
| CN109569629A (en) | The method of catalyst for acetic acid ester through hydrogenation and preparation method thereof and acetic acid ester through hydrogenation alcohol | |
| CN109092295A (en) | Isopropylbenzene catalyst and preparation method thereof | |
| CN104549323B (en) | The method of synthesis DMIZ 1,2 dimethylimidazole and loaded catalyst used | |
| CN109092301A (en) | It is used to prepare the catalyst and preparation method thereof of isopropylbenzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140730 |
|
| RJ01 | Rejection of invention patent application after publication |