CN1106219C - Supported heteropolyacid catalyst for preparing dimethyl ether by methanol dehydration and production method thereof - Google Patents
Supported heteropolyacid catalyst for preparing dimethyl ether by methanol dehydration and production method thereof Download PDFInfo
- Publication number
- CN1106219C CN1106219C CN00102506A CN00102506A CN1106219C CN 1106219 C CN1106219 C CN 1106219C CN 00102506 A CN00102506 A CN 00102506A CN 00102506 A CN00102506 A CN 00102506A CN 1106219 C CN1106219 C CN 1106219C
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- CN
- China
- Prior art keywords
- dimethyl ether
- catalyst
- hpa
- heteropoly acid
- tio
- 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.)
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 21
- 230000018044 dehydration Effects 0.000 title claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- -1 0.1-20% (m) Chemical compound 0.000 claims 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention belongs to a supported heteropoly acid composite catalyst. The invention is mainly characterized by containing a novel catalytic material, namely Heteropoly acid (HPA). The catalyst composition is HPA (1-50% (m)), and gamma-Al2O3：25-98.2%(m)，TiO2：0.1-20%(m)，La2O3: 0.1-5% (m). Prepared by an impregnation method, and the preparation conditions are as follows: the impregnation time of the active component (HPA) is 12h, the drying temperature is 120 ℃, and the roasting temperature is 350 ℃. The catalyst is used for catalyzing methanol dehydration to generate dimethyl ether. The reaction temperature is 240 ℃ and 320 ℃, the pressure is 0-1.0MPa (table), and the weight space velocity is 1.0-3.5h-1Under the reaction condition, the conversion rate of the methanol reaches 85 percent, and the selectivity of the dimethyl ether is 99.99 percent.
Description
The invention belongs to a kind of carried heteropoly acid composite catalyst, the catalysis methanol dehydration generates dimethyl ether.
The purposes of dimethyl ether is very extensive, receives the concern of developed country day by day, and it is mainly used in fields such as aerosol, civilian raw material, motor vehicle fuel, cold-producing medium and industrial chemicals.The method of producing dimethyl ether at present mainly is to be raw material with methyl alcohol, under catalyst action, makes after dehydration.Catalyst system therefor is generally aluminum phosphate [EP 169953,1986], HZSM-5 [Wu Deming etc., petrochemical industry, 1988,17 (9): 557], γ-Al
2O
3[JP 63056433,1988].The aluminum phosphate surface is coking deactivation easily, HZSM-5 cost height, γ-Al
2O
3The reaction temperature height.Because above catalyst exists self shortcoming, make the preparation of dimethyl ether, investment is big, and the cost height causes the production of dimethyl ether and use to be restricted.
The objective of the invention is to utilize the excellent specific property of heteropoly acid: highly acid (Bronsted acid and lewis acid), false property of liquid phase, there is not corrosion and pollution-free etc., make the support type composite catalyst, be used for dimethyl ether preparation by dehydrating methyl alcohol, for the preparation of dimethyl ether provide a kind of function admirable, catalyst efficiently.
The composition of catalyst:
(1) carrier: γ-Al
2O
3, mass content is 25-98.8%, is expressed as 25-98.8% (m), down together.
(2) active component:
Heteropoly acid (Hetropoly acid is abbreviated as HPA), content: 1-50% (m)
Chemical formula: HaXbMcOdnH
2O
Wherein: a:3-6 b:1-2 c:6-18 d:24-62 n:5-40; X:P, As, Sb, B, Si, Ge, Ga, In, Fe, Co etc., M:Mo, W, V, Nb etc.
(3) anti-carbon deposit component: TiO
2, content: 0.1-20% (m); La
2O
3, content: 0.1-5% (m)
Method for preparing catalyst adopts infusion process.
With γ-Al
2O
3Powder joins TiCl
4In the solution, behind placement 12～24h, use NH
3H
2O transfers pH=7.5-8.5, and agitating heating 0.5h under 50-70 ℃ of temperature after the filtration, will be deposited in 110-130 ℃ of dry 2h, compression molding.Make Al at 450-550 ℃ of roasting 2h.
2O
3-TiO
2HPA is water-soluble, add La (NO
3)
3, after the dissolving, add Al again
2O
3-TiO
2, dipping 2-24h, then at 110-130 ℃ of dry 2h, 300-400 ℃ of roasting 4h promptly gets the carried heteropoly acid composite catalyst.More than the amount calculated of the ratio described in all forming of each composition feeding quantity in catalyst add.
The carried heteropoly acid composite catalyst is used for the reaction that methanol dehydration generates dimethyl ether.Reaction equation is as follows:
Catalytic reaction is carried out in tubular reactor.At pressure is 0-1.0MPa (table), and temperature is 240-320 ℃, and weight space velocity is 1.0-3.5h
-1Under the reaction condition, methanol conversion reaches 85%, and the dimethyl ether selectivity is 99.99%.
Carried heteropoly acid composite catalyst and the present industrial catalyst CM-3-1[Lin Jing that has come into operation etc., Chemical Manufacture and technology, 1996,2:9] compare, active high, reaction temperature is low, and selectivity is good.(granularity, pressure, air speed and conversion ratio) for example under the same conditions, reaction temperature is low; For finely grained catalyst, at normal pressure, 260 ℃, air speed is 1.0h
-1Under the condition, methanol conversion improves 10%.
With immersion process for preparing carried heteropoly acid composite catalyst.Catalyst consists of HPA:1-30% (m), γ-Al
2O
355-98.2% (m), TiO
2: 0.1-10% (m), La
2O
3: 0.1-5% (m).Preparation condition is: active component (HPA) dip time is 12h, and baking temperature is 120 ℃, and sintering temperature is 350 ℃.With 5g catalyst (20-40 order), in the reaction tube of packing into, at N
2Protection is down in 400 ℃ of activation 2h.Normal pressure, weight space velocity are 1.0h
-1, under 260 ℃ of reaction conditions, methanol conversion is 77%, the dimethyl ether selectivity is 99.99%; Under pressure, weight space velocity permanence condition, in the time of 280 ℃, methanol conversion is 84%, and the dimethyl ether selectivity is 99.99%.In 15g catalyst (8-16 order) reaction tube of packing into, catalyst bed floor height 8.5cm is at N
2Protection activates 2h in 400 ℃ down.Reaction temperature: 290 ℃, pressure: 1.0MPa (table), weight space velocity: 2.0h
-1, 320 ℃ of methyl alcohol preheat temperatures, by reaction tube, methanol conversion is 83% from top to bottom, the dimethyl ether selectivity is 99.99%
Claims (2)
1, a kind of production method that is used for the carried heteropoly acid composite catalyst of methanol dehydration dimethyl ether-preparing, it is characterized in that: the composition of this catalyst mainly contains carrier: γ-Al
2O
3, 25-98.2% (m); Active component: heteropoly acid (HPA), 1-50% (m); Anti-carbon deposit component: titanium dioxide (TiO
2), 0.1-20% (m), lanthanum sesquioxide (La
2O
3), 0.1-5% (m) uses immersion process for preparing, with γ-Al
2O
3Powder joins TiCl
4In the solution, behind the placement 12-24h, use NH
3H
2O transfers pH=7.5-8.5, and agitating heating 0.5h under 50-70 ℃ of temperature after the filtration, will be deposited in 110-130 ℃ of dry 2h, and compression molding at 450-550 ℃ of roasting 2h, makes Al
2O
3-TiO
2, HPA is water-soluble, add La (NO
3)
3, after the dissolving, add Al again
2O
3-TiO
2, dipping 2-24h, then at 110-130 ℃ of dry 2h, 300-400 ℃ of roasting 4h.
2, a kind of carried heteropoly acid composite catalyst that is used for methanol dehydration dimethyl ether-preparing, it is characterized in that: the composition of this catalyst mainly contains carrier: γ-Al
2O
3, 25-98.2% (m); Active component: heteropoly acid (HPA), 1-50% (m); Anti-carbon deposit component: titanium dioxide (TiO
2), 0.1-20% (m), lanthanum sesquioxide (La
2O
3), 0.1-5% (m).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00102506A CN1106219C (en) | 2000-02-17 | 2000-02-17 | Supported heteropolyacid catalyst for preparing dimethyl ether by methanol dehydration and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00102506A CN1106219C (en) | 2000-02-17 | 2000-02-17 | Supported heteropolyacid catalyst for preparing dimethyl ether by methanol dehydration and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1308987A CN1308987A (en) | 2001-08-22 |
| CN1106219C true CN1106219C (en) | 2003-04-23 |
Family
ID=4576432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00102506A Expired - Fee Related CN1106219C (en) | 2000-02-17 | 2000-02-17 | Supported heteropolyacid catalyst for preparing dimethyl ether by methanol dehydration and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1106219C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453169C (en) * | 2007-09-29 | 2009-01-21 | 中国科学院山西煤炭化学研究所 | Catalyst for producing dimethyl ether and its preparation method and application |
| CN102463128B (en) * | 2010-11-05 | 2015-07-15 | 天门市天宝化工科技有限公司 | Preparation method for catalyst used for preparing dimethyl ether through methanol dehydration |
| CN104588056B (en) * | 2013-11-03 | 2017-07-14 | 中国石油化工股份有限公司 | Preparing dimethyl ether by dewatering methanol catalyst and preparation method thereof |
| CN104591976B (en) * | 2013-11-03 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of method of preparing dimethyl ether by dewatering methanol |
| CN104591978B (en) * | 2013-11-03 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of method of methanol dehydration dimethyl ether-preparing |
| CN104588106B (en) * | 2013-11-03 | 2017-01-18 | 中国石油化工股份有限公司 | Catalyst used for producing dimethyl ether through methanol dehydration, and preparation method thereof |
| CN104591977B (en) * | 2013-11-03 | 2016-05-18 | 中国石油化工股份有限公司 | The method of preparing dimethyl ether by dewatering methanol |
| CN104588102B (en) * | 2013-11-03 | 2017-01-25 | 中国石油化工股份有限公司 | Preparation method of catalyst used for producing dimethyl ether through methanol dehydration |
| 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 |
|---|---|---|---|---|
| CN1126717A (en) * | 1995-12-06 | 1996-07-17 | 南京师范大学 | Catalyst series for synthesizing 1-,2- and 3- substituted alkylphenols with different proportion by one-step process |
-
2000
- 2000-02-17 CN CN00102506A patent/CN1106219C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126717A (en) * | 1995-12-06 | 1996-07-17 | 南京师范大学 | Catalyst series for synthesizing 1-,2- and 3- substituted alkylphenols with different proportion by one-step process |
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| Publication number | Publication date |
|---|---|
| CN1308987A (en) | 2001-08-22 |
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