CN101700993B - Method for preparing dimethyl ether through methanol dehydration - Google Patents
Method for preparing dimethyl ether through methanol dehydration Download PDFInfo
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- CN101700993B CN101700993B CN200910197923XA CN200910197923A CN101700993B CN 101700993 B CN101700993 B CN 101700993B CN 200910197923X A CN200910197923X A CN 200910197923XA CN 200910197923 A CN200910197923 A CN 200910197923A CN 101700993 B CN101700993 B CN 101700993B
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- catalyzer
- dme
- aluminum oxide
- dimethyl ether
- niobium oxides
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Abstract
The invention relates to a method for preparing dimethyl ether through methanol dehydration. In the presence of a catalyst, the dimethyl ether is obtianed subject through methanol dehydration, and the catalyst comprises 75wt%-99.9wt% of alumina and 0.1wt%-25wt% of niobium oxide. The invention has the advantages of improving the selectivity of reactions while reducing the usage temperature of the catalyst and broadening the scale of the usage temperature. In addition, the invention eliminates carbon deposition of the catalyst substantially.
Description
Technical field
The present invention relates to a kind of preparation method of dme, specifically, relate to a kind of method by preparing bimethyl ether by catalytic dewatering of methanol.
Background technology
Dme (Dimethyl ether abridge DME) is a kind of basic Organic Chemicals, is mainly used in aspects such as daily-use chemical industry, pharmacy, refrigeration, dyestuff, coating, aerosol spraying agent.
By preparing bimethyl ether by catalytic dewatering of methanol is a kind of method for preparing dme commonly used; Catalyzer wherein commonly used has: HZSM-5 molecular sieve, dealuminzation Y molecular sieve, 12 tungstophosphoric acids or contain aluminium titanium oxide (aluminotitanate) etc., these existing catalyzer all exist use temperature narrow range and higher (use temperature of existing catalyzer generally is higher than 270 ℃), reaction preference difference or catalyst surface defectives such as " carbon distributions " easily.
Given this, provide that a kind of DME yield is high, the surperficial use temperature that is difficult for " carbon distribution " and catalyst system therefor of catalyst system therefor is low and the preparation method dme that TR is wide becomes the technical issues that need to address of the present invention.
Summary of the invention
The objective of the invention is to, provide a kind of, overcome the defective that exists in the prior art by the improving one's methods of preparing bimethyl ether by catalytic dewatering of methanol (DME).
The method for preparing dme (DME) of the present invention; Its key step is: having under the catalyzer existence condition; Obtain target compound (DME) by methyl alcohol through dehydration reaction, it is characterized in that, described catalyzer comprises: 75wt%～99.9wt% aluminum oxide and 0.1wt%～25wt% niobium oxides.
In optimal technical scheme of the present invention, used catalyzer comprises: the niobium oxides of 90wt%～99wt% aluminum oxide and 1wt%～10wt%; Preferred technical scheme is: used catalyzer comprises: the niobium oxides of 90wt%～95wt% aluminum oxide and 5wt%～10wt%.
In another optimal technical scheme of the present invention, used aluminum oxide is γ-Al
2O
3, used niobium oxides is Nb
2O
5
Embodiment
The method for preparing dme (DME) of the present invention, its reaction equation is as follows:
Said method comprises the steps:
The described catalyzer of preamble and silica sand by weight being to fill in the tubular reactor that have temperature regulating device at 1: 1, are constituted " fixed bed " formula reactor drum.Catalyst loading finishes and after nitrogen purging is somebody's turn to do " fixed bed " formula reactor drum, is warming up to 220 ℃～270 ℃.Under the 0.1Mpa condition, methyl alcohol is somebody's turn to do " fixed bed " formula reactor drum through the constant-flux pump injection, the flow of methyl alcohol is that 0.1ml/min～0.4ml/min, mass space velocity are 1h
-1～4h
-1, effusive liquid reaction product gets into the liquid receiving bottle.
A kind of method for preparing catalyzer according to the invention, its key step is: with γ-Al
2O
3Impregnated in (γ-Al in the niobium oxalate aqueous solution
2O
3The cubage of pressing described aluminum oxide of preamble and niobium oxides with the amount of niobium oxalate solution obtains); In 50 ℃～70 ℃ dippings at least 6 hours; Filter, the gained solid is prior under 110 ℃～130 ℃ conditions, drying at least 12 hours; And then after 450 ℃～550 ℃ calcinings, getting target compound (inventing said catalyzer), the specific surface of prepared catalyzer (BET) is 203m
2/ g～248m
2/ g, aperture are that 11.70nm～13.10nm, pore volume are 0.55cm
3/ g～0.80cm
3/ g, prepared catalyzer can directly use.
Wherein: being determined on the full-automatic absorption appearance of specific surface carried out, and used instrument is an ASAP2020 type specific surface area absorption appearance, adopts the N under the liquid nitrogen temperature (77K)
2Absorption method records the BET specific surface area, and sample was all handled 12 hours in 200 ℃ of vacuum outgass, calculates specific surface according to BET formula then.
Catalyzer of the present invention makes [niobium oxides (Nb except adopting dipping-calcination method
2O
5) cover (or load) at aluminum oxide (preferred γ-Al
2O
3) on] outside, can also adopt co-precipitation-calcination method (promptly adopting Tai-Ace S 150 or sodium aluminate and the niobium oxalate aqueous solution to carry out co-precipitation earlier) to make and comprise niobium oxides and aluminum oxide (preferred γ-Al then through calcining
2O
3) catalyzer.
The method for preparing dme (DME) provided by the invention; Its biggest advantage is; In the use temperature that has reduced catalyzer and widened the scope of use temperature (use temperature of catalyzer of the present invention is less than or equal to 270 ℃; Catalyzer use temperature scope is 220 ℃～270 ℃) time, the selectivity of reaction improved.In addition, " carbon distribution " phenomenon of basically eliminate catalyzer of the present invention.
Through embodiment the present invention is described further below, its purpose only is better to understand content of the present invention, and unrestricted protection scope of the present invention.
Embodiment 1
Preparation of catalysts:
Take by weighing 20 gram γ-Al
2O
3Joining concentration is 3.75 * 10
-3In the niobium oxalate solution of mol/L, in 50 ℃～70 ℃ dippings at least 6 hours, filter, the gained solid is prior to drying under 110 ℃～130 ℃ conditions at least 12 hours, and then behind the exsiccant solid, must invent said catalyzer in 450 ℃～550 ℃ calcinings.The specific surface of prepared catalyzer (BET) is 247.9m
2/ g, aperture are that 12.97nm, pore volume are 0.80cm
3/ g, wherein γ-Al
2O
3Content be 99wt%; Nb
2O
5Content be 1wt%.The preparation of dme (DME):
Above-mentioned catalyzer (4.8 gram) and silica sand by weight being to fill in the tubular reactor (internal diameter be 12mm, length be 700mm) that have temperature regulating device at 1: 1, are constituted " fixed bed " formula reactor drum.Catalyst loading finishes and after nitrogen purging is somebody's turn to do " fixed bed " formula reactor drum, is warming up to 220 ℃～270 ℃ (preferred 260 ℃).Under the 0.1Mpa condition, methyl alcohol is somebody's turn to do " fixed bed " formula reactor drum through the constant-flux pump injection, the flow of methyl alcohol is that 0.1ml/min～0.4ml/min (preferred 0.1ml/min), mass space velocity are 1h
-1～4h
-1(preferred 1h
-1), effusive liquid reaction product gets into the liquid receiving bottle.With gas chromatograph (130 ℃ of column temperature, 160 ℃ of sampler temperature, 160 ℃ of detector temperatures) analytical reaction product, according to the selectivity of material balance calculating conversion of methanol and dme, the result is following:
Methanol conversion is: 80.49%
The dme selectivity is: 100%.
Embodiment 2～9
Can prepare different catalyst with reference to embodiment 1 described method, use it for the methyl alcohol catalytic dehydration and prepare DME, its result sees table 1
Table 1
Can be known by table 1: catalyst system therefor of the present invention is still having catalytic activity and conversion of methanol higher below 240 ℃, the DME selectivity reaches 100%.And existing catalyzer is not seen catalyst activity data report below 240 ℃.In addition, catalyst system therefor of the present invention has the use temperature scope of broad, so the method for preparing dme (DME) provided by the present invention has good prospects for commercial application.
Claims (5)
1. a method for preparing dme is characterized in that, the key step of said method is: being flowed through by methyl alcohol is filled with catalyzer " fixed bed " reactor drum, behind catalytic and dehydration reaction, obtains target compound;
Wherein, described catalyzer comprises: 75wt%～99.9wt% aluminum oxide and 0.1wt%～25wt% niobium oxides; Said catalytic and dehydration reaction temperature is 220 ℃～270 ℃, and catalytic and dehydration reaction pressure is 0.1Mpa; The flow of methyl alcohol is 0.1ml/min～0.4ml/min, and mass space velocity is 1h
-1～4h
-1
2. the method for claim 1 is characterized in that, wherein said catalyzer comprises: the niobium oxides of 90wt%～99wt% aluminum oxide and 1wt%～10wt%.
3. method as claimed in claim 2 is characterized in that, wherein said catalyzer comprises: the niobium oxides of 90wt%～95wt% aluminum oxide and 5wt%～10wt%.
4. like any described method in the claim 1～3, it is characterized in that wherein said aluminum oxide is γ-Al
2O
3Said niobium oxides is Nb
2O
5
5. method as claimed in claim 4 is characterized in that the specific surface of wherein used catalyzer is: 203m
2/ g～248m
2/ g, aperture are that 11.70nm～13.10nm, pore volume are 0.55cm
3/ g～0.80cm
3/ g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910197923XA CN101700993B (en) | 2009-10-30 | 2009-10-30 | Method for preparing dimethyl ether through methanol dehydration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910197923XA CN101700993B (en) | 2009-10-30 | 2009-10-30 | Method for preparing dimethyl ether through methanol dehydration |
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| Publication Number | Publication Date |
|---|---|
| CN101700993A CN101700993A (en) | 2010-05-05 |
| CN101700993B true CN101700993B (en) | 2012-11-14 |
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ID=42155925
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|---|---|---|---|
| CN200910197923XA Expired - Fee Related CN101700993B (en) | 2009-10-30 | 2009-10-30 | Method for preparing dimethyl ether through methanol dehydration |
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| Country | Link |
|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148397A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Method for preparing dimethyl ether |
| CN101601995A (en) * | 2008-06-12 | 2009-12-16 | 中国石油化工股份有限公司 | Be used for aluminium oxide catalyst of methanol gas phase dewatering preparing dimethy ether and preparation method thereof |
-
2009
- 2009-10-30 CN CN200910197923XA patent/CN101700993B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148397A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Method for preparing dimethyl ether |
| CN101601995A (en) * | 2008-06-12 | 2009-12-16 | 中国石油化工股份有限公司 | Be used for aluminium oxide catalyst of methanol gas phase dewatering preparing dimethy ether and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN101700993A (en) | 2010-05-05 |
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