CN1613558A - Modified alumina catalyst for synthetizing dimethyl ether - Google Patents
Modified alumina catalyst for synthetizing dimethyl ether Download PDFInfo
- Publication number
- CN1613558A CN1613558A CN200410064920.6A CN200410064920A CN1613558A CN 1613558 A CN1613558 A CN 1613558A CN 200410064920 A CN200410064920 A CN 200410064920A CN 1613558 A CN1613558 A CN 1613558A
- Authority
- CN
- China
- Prior art keywords
- dimethyl ether
- methanol
- catalyst
- modification
- dehydration
- 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000003407 synthetizing effect Effects 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 96
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 22
- 230000018044 dehydration Effects 0.000 claims description 21
- 238000012986 modification Methods 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000005259 measurement Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 9
- 238000003556 assay Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 235000011837 pasties Nutrition 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A modified alumina catalyst for preparing dimethylether by dewatering methanol is prepard by adding sulfate to ordinary gamma-Al2O3. Its advantages are high transform rate and selectivity at lower temp and no carbon deposit at higher temp.
Description
One, technical field
The invention relates to a kind of modified alumina catalyst, the metal catalyst technical field by the methanol dehydration dimethyl ether synthesis.
Two, background technology
Dimethyl ether is the simplest ether, can be used as propellant, domestic fuel and diesel fuel etc., also is the important intermediate that natural gas and coal are produced liquid fuel simultaneously, is a kind of clean energy resource carrier of potentialization.
Dimethyl ether can be produced in the method that acidic catalyst dewaters by methyl alcohol, and what use the earliest is sulfuric acid, is replaced by solid acid now.The solid acid catalyst that uses has modification γ-Al
2O
3, acidic molecular sieve, aluminum phosphate etc., such as US Patent No. 4,595,785 have proposed the γ-Al with the aluminium titanates modification
2O
3Make the dehydration catalyst dimethyl ether synthesis, can improve reaction speed, can reduce side reaction and coking simultaneously, but the higher 300-400 of reaction temperature ℃; Japan Patent JP2-85224 discloses a kind of doped with II IA metal γ-Al of family
2O
3, be used for methanol dehydration dimethyl ether-preparing, it is said that this catalyst has the long life-span.
Methanol dehydration generates dimethyl ether needs acidic catalyst, and acid stronger, dehydration speed is faster, but strong excessively acidity is easy to generate the hydro carbons accessory substance, and causes coking, makes catalysqt deactivation.On the contrary, if dehydration catalyst acidity too a little less than, reach certain reaction speed temperature that must raise, this will propose higher requirement to the material of reactor.Aluminium oxide is cheap and easy to get, and as the existing report of methanol dehydration dimethyl ether-preparing catalyst (US1873537), it is used for, and Dehydration of methanol generates dimethyl ether selectivity height, accessory substance is few.But aluminium oxide is separately relatively poor as the methanol dehydration catalyst activity, and serviceability temperature is higher, thereby people explore at γ-Al
2O
3Middle other component that adds carries out modification to it, has the more γ-Al of high reaction activity with preparation
2O
3Dehydration catalyst.The modification component of adding in patent and document has aluminium titanates (US4595785), IIIA family metal (JP2-85224) and fourth officer family element (chemical industry and engineering were rolled up the 15th page of the 2nd phase in 1998 the 19th) etc.
On the other hand, the rare H of bibliographical information was once arranged
2SO
4Dipping TiO
2, ZrO
2With preparation super acids (Journal ofCatalysis, 168 volumes, 482-490 page or leaf), but do not use the sulfate doped aluminium to change the report of aluminium oxide acidity in the document.Use H in addition
2SO
4Ti, the Zr oxide acidity of modification preparation are too strong, are easy to coking, are unsuitable for as methanol dehydration catalyst.
Three, summary of the invention
The objective of the invention is common γ-Al
2O
3Carry out modification, utilize at γ-Al
2O
3The sulfate that middle adding suits is with SO
4 2-Be added to γ-Al
2O
3In, producing the acidity of moderate strength, the methanol conversion that can improve can be avoided again under the higher temperature carbon distribution on the catalyst.
The present invention uses suitable sulfate as modifying component, to γ-Al
2O
3Carry out modification, SO
4 2-Adding improved the acidity of aluminium oxide, help methanol dehydration and generate dimethyl ether.The sulfate that uses is (NH
4)
2SO
4, Al
2(SO
4)
3, Ti (SO
4)
2Deng, addition is with SO
4 2-The quality percentage composition is counted 1-4%, through the γ-Al of modification
2O
3The methanol dehydration conversion ratio reaches 79.6-91.3%, and the γ-Al of non-modified
2O
3Upper methanol dehydration conversion ratio is 35.9%.Simultaneously, because the acid site moderate strength that produces has been avoided carbon distribution on the catalyst.
Sulfate can take various ways to add, and such as infusion process, coprecipitation etc., also can add at the pilot process of alumina preparation.In the finished product that obtains after the oven dry of sample process, the roasting, SO
4 2-Suitable quality percentage composition is 1-4%.
Used aluminium oxide is γ-Al
2O
3
Four, inventive embodiments
Following embodiment is in order to further specify catalyst of the present invention:
Embodiment 1: take by weighing Ti (SO
4)
250.0g, add 3000ml distilled water, stirring and dissolving, other takes by weighing commercially available powdery γ-Al
2O
3(A: specific area 290m
2/ g) 950.0g pours above-mentioned Ti (SO into
4)
2In the solution, stir and be pasty state.Placed 5 hours under the room temperature, 110 ℃ of oven dry 12 hours, made Ti (SO in 1.5 hours 450 ℃ of roastings at last then
4)
2Modification γ-Al
2O
3Modification γ-the Al that obtains thus
2O
3Contain SO
4 2-4wt%, through compressing tablet, smash, sieving is the 20-40 order, is used for the reaction of preparing dimethyl ether from methanol by dehydration performance measurement.Assay method: take by weighing catalyst sample 0.5g of the present invention, put into glass reaction tube, be heated to 260 ℃, import reactor being preheating to 260 ℃ behind the methanol gasifying, analysis reactor import methanol concentration and exit gas are formed, and calculate methanol conversion and dimethyl ether selectivity.Measurement result: methanol conversion is 91.3%, dimethyl ether selectivity 100%.
Embodiment 2: take by weighing (NH
4)
2SO
427.1g, add 2000ml distilled water, stirring and dissolving, other takes by weighing powdery γ-Al
2O
3(A: specific area 290m
2/ g) 490.0g pours above-mentioned (NH into
4)
2SO
4In the solution, stir and be pasty state.Placed 5 hours under the room temperature, 110 ℃ of oven dry 12 hours, made (NH in 1.5 hours 450 ℃ of roastings at last then
4)
2SO
4Modification γ-Al
2O
3Modification γ-the Al that obtains thus
2O
3Contain SO
4 2-4wt%, through compressing tablet, smash, sieving is the 20-40 order, is used for the reaction of preparing dimethyl ether from methanol by dehydration performance measurement, assay method is with embodiment 1.Measurement result: methanol conversion is 90.7%, dimethyl ether selectivity 100%.
Embodiment 3: take by weighing Ti (SO
4)
212.5g, add 3000ml distilled water, stirring and dissolving, other takes by weighing powdery γ-Al
2O
3(A: specific area 290m
2/ g) 990.0g pours above-mentioned Ti (SO into
4)
2In the solution, stir and be pasty state.Placed 5 hours under the room temperature, 110 ℃ of oven dry 12 hours, made Ti (SO in 1.5 hours 450 ℃ of roastings at last then
4)
2Modification γ-Al
2O
3Modification γ-the Al that obtains thus
2O
3Contain SO
4 2-1wt%, through compressing tablet, smash, sieving is the 20-40 order, is used for the reaction of preparing dimethyl ether from methanol by dehydration performance measurement, assay method is with embodiment 1.Measurement result: methanol conversion is 79.6%, dimethyl ether selectivity 100%.
Embodiment 4: take by weighing Ti (SO
4)
250.0g, add 3000ml distilled water, stirring and dissolving, other takes by weighing powdery γ-Al
2O
3(B: specific area 180m
2/ g) 950.0g pours above-mentioned Ti (SO into
4)
2In the solution, stir and be pasty state.Placed 5 hours under the room temperature, 110 ℃ of oven dry 12 hours, made Ti (SO in 1.5 hours 450 ℃ of roastings at last then
4)
2Modification γ-Al
2O
3
Modification γ-the Al that obtains thus
2O
3Contain SO
4 2-4wt%, through compressing tablet, smash, sieving is the 20-40 order, is used for the reaction of preparing dimethyl ether from methanol by dehydration performance measurement, assay method is with embodiment 1.Measurement result: methanol conversion is 90.8%, dimethyl ether selectivity 100%.
Embodiment 5: take by weighing Al
2(SO
4)
318H
2O93g adds 1800ml distilled water, stirring and dissolving, and other takes by weighing powdery γ-Al
2O
3(A: specific area 290m
2/ g) 937.0g pours above-mentioned Al into
2(SO
4)
3In the solution, stir and be pasty state.Placed 5 hours under the room temperature, 110 ℃ of oven dry 12 hours, made Al in 1.5 hours 450 ℃ of roastings at last then
2(SO
4)
3Modification γ-Al
2O
3Modification γ-the Al that obtains thus
2O
3Contain SO
4 2-4wt%, through compressing tablet, smash, sieving is the 20-40 order, is used for the reaction of preparing dimethyl ether from methanol by dehydration performance measurement, assay method is with embodiment 1.Measurement result: methanol conversion is 86.0%, dimethyl ether selectivity 100%.
Table 1 is listed the SO of the catalyst of embodiment 1-5
4 2-Content and corresponding methanol dehydration conversion ratio and dimethyl ether selectivity.As a comparison, list file names with unmodified γ-Al under the same terms
2O
3The methanol dehydration measurement result.
Table 1. methanol conversion and dimethyl ether selective (260 ℃, normal pressure, methanol liquid air speed 1.5h
-1)
| SO 4 2-Content/wt% | Methanol conversion/% | Dimethyl ether is selective/% | |
| Embodiment 1 | 4 | 91.3 | 100 |
| Embodiment 2 | 4 | 90.7 | 100 |
| Embodiment 3 | 1 | 79.6 | 100 |
| Embodiment 4 | 4 | 90.8 | 100 |
| Embodiment 5 | 4 | 86.0 | 100 |
| Reference | 0 | 35.9 | 100 |
Claims (2)
1. for the synthesis of the modified alumina catalyst of dimethyl ether, use γ-Al
2O
3As the catalyst of methanol dehydration dimethyl ether synthesis, it is characterized in that adding sulfate to γ-Al
2O
3Modification, suitable sulfate has (NH
4)
2SO
4, Al
2(SO
4)
3, Ti (SO
4)
2
2. the modified alumina catalyst that is used for dimethyl ether synthesis according to claim 1, the quality percentage composition that it is characterized in that sulfate in the modified aluminas is with SO
4 2-Count 1-4%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410064920.6A CN1613558A (en) | 2004-10-12 | 2004-10-12 | Modified alumina catalyst for synthetizing dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410064920.6A CN1613558A (en) | 2004-10-12 | 2004-10-12 | Modified alumina catalyst for synthetizing dimethyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1613558A true CN1613558A (en) | 2005-05-11 |
Family
ID=34764598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410064920.6A Pending CN1613558A (en) | 2004-10-12 | 2004-10-12 | Modified alumina catalyst for synthetizing dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1613558A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374203C (en) * | 2006-04-13 | 2008-03-12 | 中国科学院大连化学物理研究所 | Homogeneous temperature type catalyst for preparing dimethyl ether from methanol and use |
| CN100379491C (en) * | 2006-07-21 | 2008-04-09 | 新奥新能(北京)科技有限公司 | Catalyst for preparing dimethyl ether by methanol dehydration and its preparation method |
| CN101602006B (en) * | 2008-06-12 | 2011-05-18 | 中国石油化工股份有限公司 | Modified aluminum oxide catalyst for synthesizing dimethyl ether and preparation method thereof |
| CN102372582A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Fluidized catalytic method for toluene methylation |
| CN102633611A (en) * | 2012-03-28 | 2012-08-15 | 南开大学 | Method of using modified alumina catalyst to continuously prepare methyl vinyl ketone |
| CN106179403A (en) * | 2016-06-27 | 2016-12-07 | 巨化集团技术中心 | A kind of catalyst of synthesis 2,3,3,3 tetrafluoropropenes and its production and use |
| CN106607060A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst and its preparation method and application, and method for preparing ethanediamine through ethylene glycol hydrogenation amination |
| CN112592271A (en) * | 2020-12-22 | 2021-04-02 | 河北兴柏农业科技有限公司 | Method and device for preparing isooctyl acrylate |
-
2004
- 2004-10-12 CN CN200410064920.6A patent/CN1613558A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374203C (en) * | 2006-04-13 | 2008-03-12 | 中国科学院大连化学物理研究所 | Homogeneous temperature type catalyst for preparing dimethyl ether from methanol and use |
| CN100379491C (en) * | 2006-07-21 | 2008-04-09 | 新奥新能(北京)科技有限公司 | Catalyst for preparing dimethyl ether by methanol dehydration and its preparation method |
| CN101602006B (en) * | 2008-06-12 | 2011-05-18 | 中国石油化工股份有限公司 | Modified aluminum oxide catalyst for synthesizing dimethyl ether and preparation method thereof |
| CN102372582A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Fluidized catalytic method for toluene methylation |
| CN102633611A (en) * | 2012-03-28 | 2012-08-15 | 南开大学 | Method of using modified alumina catalyst to continuously prepare methyl vinyl ketone |
| CN106607060A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst and its preparation method and application, and method for preparing ethanediamine through ethylene glycol hydrogenation amination |
| CN106607060B (en) * | 2015-10-26 | 2019-08-20 | 中国石油化工股份有限公司 | Catalyst and its preparation method and application and ethylene glycol face the method for hydrogen amination ethylenediamine |
| CN106179403A (en) * | 2016-06-27 | 2016-12-07 | 巨化集团技术中心 | A kind of catalyst of synthesis 2,3,3,3 tetrafluoropropenes and its production and use |
| CN112592271A (en) * | 2020-12-22 | 2021-04-02 | 河北兴柏农业科技有限公司 | Method and device for preparing isooctyl acrylate |
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