CN100579651C - Catalyst for synthesizing dimethyl ether and preparation method - Google Patents
Catalyst for synthesizing dimethyl ether and preparation method Download PDFInfo
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- CN100579651C CN100579651C CN200810012501A CN200810012501A CN100579651C CN 100579651 C CN100579651 C CN 100579651C CN 200810012501 A CN200810012501 A CN 200810012501A CN 200810012501 A CN200810012501 A CN 200810012501A CN 100579651 C CN100579651 C CN 100579651C
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Abstract
The present invention relates to a catalyst used for synthesizing dimethyl ether and a preparation method thereof which belong to the chemical catalyst and the preparation field. The main components of the catalyst used for synthesizing the dimethyl ether are active Al2O3 and element C, wherein, the weight percentage of the active Al2O3 is 97 percent to 99 percent, and the weight percentage of the element C is 1 percent to 3 percent. Compared with similar catalyst, the catalyst has wide reaction temperature range, high selectivity, no caking easily, obviously improved stability and greatly prolonged service live.
Description
Technical field
The present invention relates to a kind of dimethyl ether synthetic catalyst and preparation method of being used for, belong to chemical catalyst and preparation field thereof.
Background technology
Dimethyl ether is important chemical material and liquid fuel, and consumption is big, development is fast.The general methanol dehydration technology that adopts is produced, and catalyst adopts activated alumina, molecular sieve etc. mostly.
Chinese patent CN1036199A discloses a kind of method by the methanol production dimethyl ether, and methanol gas is carried out dehydration containing on the activated alumina of a small amount of SiO2; Chinese patent CN1125216 adopts and contains aluminium oxide and alumino-silicate and composite solid-acid catalyst; Chinese patent CN1106219C discloses a kind of alumina load heteropolyacid catalyst; Chinese patent application 200410064920.6 discloses a kind of aluminium oxide catalyst with the sulfate modification.
Summary of the invention
The objective of the invention is to develop a kind of dimethyl ether synthetic catalyst and preparation method of being used for, it should be the dimethyl ether catalyst of a kind of high selectivity, high stability.
The technical solution adopted for the present invention to solve the technical problems is: a kind of synthetic method for preparing catalyst of dimethyl ether that is used for, the main component of described catalyst is active A l
2O
3With the C element, active A l wherein
2O
3Mass percent be 97-99%, the mass percent of C element is 1-3%.Active A l with moulding
2O
3With the dipping of the manganese acetate in the formic acid in the organic acid, glacial acetic acid or the acylate, after the drying, under inert gas shielding, carry out roasting, obtain the active A l of C modification
2O
3The general dilute aqueous that adopts of organic acid or acylate dipping is preferably under the vacuum and floods.
The invention has the beneficial effects as follows: this main component that is used for the synthetic catalyst of dimethyl ether is active A l
2O
3With the C element, active A l wherein
2O
3Mass percent be 97-99%, the mass percent of C element is 1-3%.This catalyst is compared with similar catalyst, reaction wide temperature region, selectivity height, be difficult for that knot charcoal, stability obviously improve, prolong service life greatly.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
(1) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing the 7g glacial acetic acid and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 1.2%.
(2) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing the 10g glacial acetic acid and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 1.6%.
(3) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing the 10g manganese acetate and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 1.3%.
(4) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing 12g formic acid and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 1.2%.
(5) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing 25g formic acid and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 2.1%.
(6) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing 36g formic acid and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 3.2%.
(7) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing 48g formic acid and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 4.3%.
(8) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing 55g formic acid and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 4.7%.
(9) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing 6g formic acid and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 0.5%.
(10) diameter 0.5-1mm alumina balls are put into calcining furnace, and are 500 ℃ of calcinings 3 hours, standby.Get the 200g alumina balls and put into the vacuum impregnation still; Take by weighing 2g formic acid and be dissolved in the 100g water, open the vacuum impregnation still, with the acetum thorough impregnation on aluminium oxide.
Alumina balls are taken out,, under nitrogen protection,, take out after reducing to normal temperature in 550 ℃ of calcinings 6 hours in 100-120 ℃ of dry 5-8 hour.Testing its C content is 0.2%
Comparative example:
(1) diameter 0.5-1mm alumina balls were put into calcining furnace, 550 ℃ of calcinings 6 hours.
The foregoing description and comparative example all adopt with a kind of aluminium oxide, and its specific area is 280m
2/ g, bulk density position 0.65g/ml.
Performance to catalyst on the 20ml reaction unit is estimated, and the active testing condition is: 300 ℃ of temperature, and pressure 0.8Mpa, the methanol liquid air speed is 1.5h
-1
In order to predict the stability of catalyst, catalyst is carried out high temperature, high-speed, and to accelerate carbon deposit aging, and condition is: 470 ℃ of temperature, and pressure 0.8Mpa, the methanol liquid air speed is 5.5h
-1Time is 8 hours.And then under normal condition, survey its activity.
Table-1 catalyst activity, selectivity, stability test result
| Initial activity (%) | Selectivity (%) | Aging back active (%) | |
| Embodiment 1 | 83.5 | 99.99 | 70.2 |
| 2 | 82.1 | 99.99 | 72.5 |
| 3 | 81.1 | 99.99 | 72.0 |
| 4 | 83.2 | 99.99 | 71.8 |
| 5 | 79.6 | 99.99 | 73.3 |
| 6 | 74.3 | 99.99 | 69.2 |
| 7 | 70.7 | 99.99 | 69.0 |
| 8 | 69.8 | 99.99 | 68.8 |
| 9 | 83.2 | 99.95 | 59.6 |
| 10 | 83.7 | 99.90 | 50.1 |
| Comparative example 1 | 84.2 | 99.80 | 45.7 |
From table-1 data as can be seen, adopt the prepared catalyst of the present invention, be used for the reaction of methanol gas phase dehydration dimethyl ether synthesis, the selectivity of reaction brings up to 99.99% from 99.8%, and the stability of catalyst is greatly improved.
Claims (1)
1, a kind of synthetic method for preparing catalyst of dimethyl ether that is used for, the main component of described catalyst is active A l
2O
3With the C element, active A l wherein
2O
3Mass percent be 97-99%, the mass percent of C element is 1-3%; It is characterized in that: with the active A l of moulding
2O
3With the dipping of the manganese acetate in the formic acid in the organic acid, glacial acetic acid or the acylate, after the drying, under inert gas shielding, carry out roasting, obtain the active A l of C modification
2O
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810012501A CN100579651C (en) | 2008-07-23 | 2008-07-23 | Catalyst for synthesizing dimethyl ether and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810012501A CN100579651C (en) | 2008-07-23 | 2008-07-23 | Catalyst for synthesizing dimethyl ether and preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN101327426A CN101327426A (en) | 2008-12-24 |
| CN100579651C true CN100579651C (en) | 2010-01-13 |
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|---|---|---|---|
| CN200810012501A Active CN100579651C (en) | 2008-07-23 | 2008-07-23 | Catalyst for synthesizing dimethyl ether and preparation method |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383946A (en) * | 2014-10-20 | 2015-03-04 | 大连瑞克科技有限公司 | Catalyst for preparation of dimethyl ether by gas phase dehydration of methanol and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4595785A (en) * | 1983-06-16 | 1986-06-17 | E. I. Dupont De Nemours And Company | Preparation of dimethyl ether by catalytic dehydration of methanol |
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2008
- 2008-07-23 CN CN200810012501A patent/CN100579651C/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4595785A (en) * | 1983-06-16 | 1986-06-17 | E. I. Dupont De Nemours And Company | Preparation of dimethyl ether by catalytic dehydration of methanol |
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| CN101327426A (en) | 2008-12-24 |
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