CN101024165A - Novel gamma aluminium oxide catalyst and producing technology - Google Patents
Novel gamma aluminium oxide catalyst and producing technology Download PDFInfo
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- CN101024165A CN101024165A CN 200710048718 CN200710048718A CN101024165A CN 101024165 A CN101024165 A CN 101024165A CN 200710048718 CN200710048718 CN 200710048718 CN 200710048718 A CN200710048718 A CN 200710048718A CN 101024165 A CN101024165 A CN 101024165A
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Abstract
The invention discloses a new typeGama-alumina catalyst, the characteristic lie in: specific surface reaches to 300m2/g, strength reaches to 4daN, hole contain reaches to 1.35cm3/g, the pore volume distribution of the aperture 3-10nm pore is more than 80%. It supplies a new typeGama-alumina catalyst preparation method, the characteristics are: in 70 to 80 deg.C temperature, carbon dioxide gas into sodium metaaluminate solution of aluminum base rate 1.0-2.0 to the carbonation, control Solution between pH9.8 -10.5, the aluminum hydroxide powder slowly formed; the gelling time is 100-140 minutes, stirring slowly to 10 to 14 hours; then after separation aluminum powder, washing, drying, crushing, Kneading shape, 500 ~ 700deg.C baking it becomes a Gama - alumina catalyst.
Description
Technical field
The present invention relates to a kind of novel dimethyl ether catalyst, be specifically related to a kind of manufacture craft of novel gamma aluminium oxide catalyst.
Background technology
Dimethyl ether (DME) is the simplest a kind of ethers, and is of many uses, can be used as the propellant of refrigerant, solvent, extractant, aerosol.In addition, owing to self contain oxygen, sufficient combustion, dimethyl ether has extremely wide application prospect at domestic fuel and vehicle fuel field, is described as " clean fuel of 21 century ".
The industrial production of dimethyl ether generally is raw material with methyl alcohol, forms (two step method) through the gas and solid phase catalyzing dehydration, and catalyst system therefor comprises: gama-alumina, molecular sieve, sial composite catalyst, carried molecular sieve or aluminium oxide etc.Wherein, gama-alumina catalytic activity height, negative product is few, the life-span is long, energy consumption is low, has very strong competitiveness.
As the catalyst of preparing dimethyl ether by dewatering methanol, generally require gama-alumina to have lower Na
2O content is than Large ratio surface and pore volume and uniformly middle pore size distribution.
European patent EP 1396483A1 discloses a kind of gamma-alumina catalyst that is used for preparing dimethyl ether by dewatering methanol, its Na
2O content is lower than 0.07%, and pore-size distribution is between 2.5～8nm.
Japan Patent JP-A-03-056433 is that specific surface is 210～300m to the requirement of the gamma-alumina catalyst of preparing dimethyl ether by dewatering methanol
2/ g, more preferably specific surface is 230～290m
2/ g, the accumulative total pore volume in the following hole of 30nm requires to reach 0.60～0.90cm
3/ g, average pore size is 5～10nm, more preferably average pore size is 5～8.5nm.
Reduce Na
2It is enough for the method for O content, comprises washing, and weak acid is washed, ammonium nitrate, ammonium sulfate, ammonium chloride etc.These methods generally can both be with the Na in the catalyst raw material
2O content is reduced to the level that needs.
The existing method that improves aluminium oxide catalyst or carrier specific area and pore volume is added surfactant or expanding agent and is often used except factors such as control PH, temperature, sinking speed.
(Zhu Hongfa writes " catalyst carrier preparation and application technology ", Beijing: petroleum industry publishing house, 2002.5) summarized the various expanding agents that adopted in present industrial production and the research in the book, comprising: polyethylene glycol, polyoxyethylene, cellulose, starch, cellulose derivative, polyvinyl alcohol and polyacrylamide etc.These expanding agents add in the aluminum hydroxide precipitation process, stay hole after the roasting, thereby reach the effect of reaming and increase specific area.But, the used expanding agent consumption of above-mentioned technology generally very big (5～50%), thereby cause the increase of cost of manufacture, simultaneously, the adding of large amount of organic causes aluminium oxide catalyst intensity to descend, the aluminium oxide catalyst pore-size distribution that what is more important in this way obtains is wide, can not be used for the catalyst of preparing dimethyl ether by dewatering methanol.
The addition manner of another expanding agent is to introduce reaming material such as organic matter in the shaped catalyst process.This method also causes the expanding agent skewness easily except the shortcoming with above-mentioned expanding agent, produce super big hole.
CN1803618A discloses a kind of method for preparing the mesopore gama-alumina: with aluminium colloidal sol is precursor, add surfactant, high molecular polymer or carboxylic acid are done structure directing agent, add alkali and regulate PH8～11,80～100 ℃ of following hydro-thermals are synthetic, form gama-alumina after separation, washing, drying, 500 ℃ of following roastings.The gama-alumina specific surface 290～350m of preparation
2/ g, pore volume 0.4cm
3More than/the g, average pore size 4～10nm.The advantage of this method is an even aperture distribution, but pore volume is less than normal, and activity is lower when doing dimethyl ether catalyst.
CN1179356A also discloses a kind of preparation method of mesopore gama-alumina: in the aluminum oxide dry glue powder kneading process, elder generation adds certain amount of alkaline solution, adds a certain amount of acid solution again after fully mixed the pinching, and extrusion shaping then, drying, roasting form.This catalyst specific surface 290～350m
2/ g, pore volume 0.65～0.88cm
3/ g, 7～13nm pore volume account for total pore volume 80～98%.This method has been destroyed the alumina surface acid site, thereby Dehydration of methanol has been caused harmful effect owing to add acid-base material repeatedly.
Summary of the invention
Technical problem to be solved by this invention be how to provide a kind of have high activity, high selectivity, making easily, can satisfy the gamma-alumina catalyst and the manufacture craft thereof of the preparing dimethyl ether by dewatering methanol of industrial requirement.
Technical problem proposed by the invention is to solve like this: a kind of novel gamma aluminium oxide catalyst is provided, it is characterized in that: specific surface reaches 300m
2/ g, intensity reaches 4daN, and pore volume reaches 1.35cm
3/ g, the aperture is that the pore volume distribution in 3～10nm hole accounts for more than 80%.
A kind of preparation method of above-mentioned novel gamma aluminium oxide catalyst is provided, it is characterized in that: under 70～80 ℃ of temperature, it is in 1.0～2.0 the sodium aluminate solution that carbon dioxide is introduced the alkali aluminum ratio, carry out carburizing reagent, between the control solution PH 9.8～10.5, the aluminium hydroxide rubber powder is slowly formed; Become slowly to add in the glue process weight ratio and be 1～2% template agent guiding have good in the formation of aluminium glue of pore size distribution, gelation time 100～140 minutes continues slowly to stir 10～14 hours; With the separation of aluminium glue powder, washing, drying, pulverizing, kneading shaping, become gamma-alumina catalyst after 500～700 ℃ of following roastings then.
Preparation method according to novel gamma aluminium oxide catalyst provided by the present invention, it is characterized in that: described template agent is the organic polymer material with dendritic structure of N element and C element or their mixture, concrete as diaminourea propyl group tetra-methylenedimine, N, N '-two (3-aminopropyl)-ethylenediamine, spiroperidol, amino acid etc., form in the precipitation process at aluminium hydroxide, the formation of its pore structure that leads, thus realize high-ratio surface, large pore volume, have evenly in the formation of aluminium hydroxide rubber powder of pore size distribution.
Advantage of the present invention is: catalyst of the present invention has good preparing dimethyl ether by dewatering methanol activity and selectivity, and conversion per pass reaches more than 75%, and selectivity reaches more than 99.5%, is fit to industrial production.
The specific embodiment
The present invention is further illustrated for following embodiment.
Wherein, the XRD test adopts X ' pert MPD to fly sharp spectrum X-ray diffractometer, and detection method is abideed by JY/T009-1996 changes target polycrystal X-ray diffraction method general rule.
The JEM-100CXII projection electron microscope is adopted in the SEM test, and detection method is abideed by TEM operation standard standard, rules: JY/T011-1996 perspective electron microscope method general rule.
JW-K pore-size distribution and specific surface analyzer are adopted in specific area, pore volume, pore-size distribution test.
The evaluating catalyst condition is: air speed 1700/h-, and 320 ℃ of reaction temperatures, pressure 1.0mPa, product directly enters analytical instrument from reactor outlet and analyzes methanol conversion and dimethyl ether selectivity.
The instrument that product analysis is adopted is: the HP5890 gas-chromatography.
Example one: with diaminourea propyl group tetra-methylenedimine is that the template agent prepares the gama-alumina dimethyl ether catalyst
1000ml four neck flasks are installed on the magnetic stirring apparatus of charged heating and precision temperature control, add 200g deionized water and template agent 1.8g diaminourea propyl group tetra-methylenedimine to flask; Online acidity assaying instrument, dropper are installed, the carbon dioxide bubbling device is installed; Heat up, stir, the control solution temperature is 70 ℃, and mixing speed is 100rpm; Slowly open dropper, 450g20% sodium aluminate solution (alkali aluminum ratio 1.15) is slowly splashed in the flask, open the carbon dioxide bubbling device, regulate carbon dioxide bubbling speed, controlling whole process PH is between 9.8～10.5, and carbonisation was finished in 2 hours; Take off the carbon dioxide bubbling device, reflux is installed, is continued to keep temperature to form aluminum hydroxide sol in 12 hours, filter, with pure water cyclic washing filter cake until PH=6.5～7.5, filter cake is taken off, be placed on oven dry in 3 hours in the baking oven, mediate with 4% nitric acid immediately, extrusion is shaped, dried again 3 hours, and be placed on 600 ℃ Muffle furnace roasting 4 hours, obtain gama-alumina dimethyl ether catalyst (being numbered 1#).The gained catalyst is carried out the SEM perspective, XRD scanning, BET test pore volume, specific surface, pore-size distribution.
Example two: prepare the gama-alumina dimethyl ether catalyst for the template agent with the spiroperidol
Change the template agent into the 1.5g spiroperidol, prepare gama-alumina dimethyl ether catalyst (being numbered 2#) according to the method identical with example one.
Example three: the mixture with diaminourea propyl group tetra-methylenedimine and spiroperidol is that the template agent prepares the gama-alumina dimethyl ether catalyst
Change the template agent into 0.9g diaminourea propyl group tetra-methylenedimine+0.9g spiroperidol, prepare gama-alumina dimethyl ether catalyst (being numbered 3#) according to the method identical with example one.
Example four: Comparative Examples
Do not add any template agent, prepare gama-alumina dimethyl ether catalyst (being numbered 4#) according to the method for example one.
The gama-alumina dimethyl ether catalyst performance data table of table 1 different templates agent preparation
| The catalyst sequence number | Template agent and consumption | Specific area (m 2/g) | Pore volume (cm 3/g) | 3～10nm pore volume accounting example | Intensity (daN) |
| ?1# | Diaminourea propyl group tetra-methylenedimine, 2% | 324 | ?1.41 | ?82 | ?4.5 |
| ?2# | Spiroperidol, 1.6% | 317 | ?1.36 | ?85 | ?4.2 |
| ?3# | Diaminourea propyl group tetra-methylenedimine, 1% spiroperidol, 1% | 330 | ?1.45 | ?89 | ?4.9 |
| ?4# | Do not have | 248 | ?0.46 | ?45 | ?4.8 |
Each the gama-alumina dimethyl ether catalyst catalytic performance contrast of table 2 different templates agent system
| The catalyst sequence number | Condition | Methanol conversion (%) | Dimethyl ether selectivity (%) | ||
| Temperature (℃) | Pressure (MPa) | Air speed (Nm 3/m 3.h) | |||
| ?1# | 300～320 | ?0.9～1.0 | ?1700 | ?82 | ＞99.5 |
| ?2# | 300～320 | ?0.9～1.0 | ?1700 | ?78 | ＞99.5 |
| ?3# | 300～320 | ?0.9～1.0 | ?1700 | ?83 | ＞99.5 |
| ?4# | 300～320 | ?0.9～1.0 | ?1700 | ?68 | ＞99.5 |
Claims (4)
1, a kind of preparation method of novel gamma aluminium oxide catalyst, it is characterized in that: under 70～80 ℃ of temperature, it is in 1.0～2.0 the sodium aluminate solution that carbon dioxide is introduced the alkali aluminum ratio, carries out carburizing reagent, between the control solution PH 9.8～10.5, the aluminium hydroxide rubber powder is slowly formed; Become slowly to add in the glue process weight ratio and be 1～2% template agent guiding have good in the formation of aluminium glue of pore size distribution, gelation time 100～140 minutes continues slowly to stir 10～14 hours; With the separation of aluminium glue powder, washing, drying, pulverizing, kneading shaping, become gamma-alumina catalyst after 500～700 ℃ of following roastings then.
2, the preparation method of novel gamma aluminium oxide catalyst according to claim 1 is characterized in that: described template agent is the organic polymer material with dendritic structure of N element and C element or their mixture.
3, the preparation method of novel gamma aluminium oxide catalyst according to claim 2, it is characterized in that: described template agent can be diaminourea propyl group tetra-methylenedimine, N, a kind of in N '-two (3-aminopropyl)-ethylenediamine, spiroperidol, the amino acid.
4, according to the prepared novel gamma aluminium oxide catalyst of the arbitrary described preparation method of claim 1～3, it is characterized in that: specific surface reaches 300m
2/ g, intensity reaches 4daN, and pore volume reaches 1.35cm
3/ g, the aperture is that the pore volume distribution in 3～10nm hole accounts for more than 80%.
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| CNB2007100487188A CN100522349C (en) | 2007-03-26 | 2007-03-26 | Novel gamma aluminium oxide catalyst and producing technology |
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| CNB2007100487188A CN100522349C (en) | 2007-03-26 | 2007-03-26 | Novel gamma aluminium oxide catalyst and producing technology |
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| CN101024165A true CN101024165A (en) | 2007-08-29 |
| CN100522349C CN100522349C (en) | 2009-08-05 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597077B (en) * | 2009-07-09 | 2012-04-25 | 南开大学 | Method for synthesizing mesoporous alumina |
| CN102448912A (en) * | 2009-05-29 | 2012-05-09 | 赢创奥克森诺有限责任公司 | Production of 3-methylbut-1-en by means of dehydration of 3-methylbutane-1-ol |
| CN106984296A (en) * | 2017-04-24 | 2017-07-28 | 西南化工研究设计院有限公司 | A kind of preparation method of new gas phase Division A League Matches of French Football alcohol catalyst for producing dimethyl ether |
| CN111375418A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN114433119A (en) * | 2020-10-30 | 2022-05-06 | 中国科学院宁波材料技术与工程研究所 | Heavy aromatic oil hydrofining catalyst and method for producing BTX (benzene-toluene-xylene) from heavy aromatic oil |
| CN114433111A (en) * | 2020-10-30 | 2022-05-06 | 宁波中金石化有限公司 | Heavy aromatic oil hydrofining catalyst and heavy aromatic oil processing method |
| CN114433118A (en) * | 2020-10-30 | 2022-05-06 | 中国科学院宁波材料技术与工程研究所 | Fluidized bed hydrogenation catalyst and processing method of coal tar whole fraction |
| CN115745016A (en) * | 2021-09-07 | 2023-03-07 | 浙江海创锂电科技有限公司 | Continuous preparation method of gradient NCM @ NCMA high-nickel precursor |
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2007
- 2007-03-26 CN CNB2007100487188A patent/CN100522349C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102448912A (en) * | 2009-05-29 | 2012-05-09 | 赢创奥克森诺有限责任公司 | Production of 3-methylbut-1-en by means of dehydration of 3-methylbutane-1-ol |
| CN101597077B (en) * | 2009-07-09 | 2012-04-25 | 南开大学 | Method for synthesizing mesoporous alumina |
| CN106984296A (en) * | 2017-04-24 | 2017-07-28 | 西南化工研究设计院有限公司 | A kind of preparation method of new gas phase Division A League Matches of French Football alcohol catalyst for producing dimethyl ether |
| CN106984296B (en) * | 2017-04-24 | 2019-06-18 | 西南化工研究设计院有限公司 | A kind of preparation method of vapor phase method methyl alcohol to dimethyl ether catalyst |
| CN111375418A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN111375418B (en) * | 2018-12-28 | 2022-09-09 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN114433111A (en) * | 2020-10-30 | 2022-05-06 | 宁波中金石化有限公司 | Heavy aromatic oil hydrofining catalyst and heavy aromatic oil processing method |
| CN114433118A (en) * | 2020-10-30 | 2022-05-06 | 中国科学院宁波材料技术与工程研究所 | Fluidized bed hydrogenation catalyst and processing method of coal tar whole fraction |
| CN114433119A (en) * | 2020-10-30 | 2022-05-06 | 中国科学院宁波材料技术与工程研究所 | Heavy aromatic oil hydrofining catalyst and method for producing BTX (benzene-toluene-xylene) from heavy aromatic oil |
| CN114433119B (en) * | 2020-10-30 | 2023-06-02 | 中国科学院宁波材料技术与工程研究所 | Heavy aromatic oil hydrofining catalyst and method for producing BTX from heavy aromatic oil |
| CN114433118B (en) * | 2020-10-30 | 2023-06-02 | 中国科学院宁波材料技术与工程研究所 | Ebullated bed hydrogenation catalyst and method for processing coal tar full fraction |
| CN114433111B (en) * | 2020-10-30 | 2023-08-25 | 宁波中金石化有限公司 | Heavy aromatic oil hydrofining catalyst and heavy aromatic oil processing method |
| CN115745016A (en) * | 2021-09-07 | 2023-03-07 | 浙江海创锂电科技有限公司 | Continuous preparation method of gradient NCM @ NCMA high-nickel precursor |
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| CN100522349C (en) | 2009-08-05 |
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