CN104588060A - Catalyst used for preparing dimethyl ether through methanol dehydration, and preparation method thereof - Google Patents
Catalyst used for preparing dimethyl ether through methanol dehydration, and preparation method thereof Download PDFInfo
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- CN104588060A CN104588060A CN201310532029.XA CN201310532029A CN104588060A CN 104588060 A CN104588060 A CN 104588060A CN 201310532029 A CN201310532029 A CN 201310532029A CN 104588060 A CN104588060 A CN 104588060A
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Abstract
The invention discloses a catalyst used for preparing dimethyl ether (DME) through methanol dehydration, and a preparation method thereof. According to the catalyst, alumina is adopted as a carrier, an active component is heteropolyacid ammonium salt, and an auxiliary agent is lanthanum oxide and/or cerium oxide. The preparation method has the following steps: the alumina carrier is added into an organic acid water solution solution containing the auxiliary agent; the mixture is evaporated to dryness; the obtained substance is added into an ammonium-containing alkaline solution or contacts ammonia gas; drying is carried out, and the obtained substance is added into a water solution of heteropolyacid; the mixture is evaporated to dryness; and drying and roasting are carried out, such that the catalyst is obtained. The catalyst provided by the invention has relatively high activity, selectivity and coke resistance. Also, catalyst stability is improved. The catalyst provided by the invention is especially suitable for a reaction for preparing dimethyl ether through the dehydration of a methanol raw material with relatively high water content.
Description
Technical field
The present invention relates to a kind of dimethyl ether by methanol dewater and preparation method thereof, particularly relate to a kind of carried heteropoly acid ammonium salt in catalysis agent for preparing dimethyl ether by dewatering methanol and preparation method thereof.
Background technology
Dimethyl ether (Dimethy Ether, abbreviation DME) is a kind of colourless, non-toxic gas under normal temperature and pressure state, can compressedly be liquid.Dimethyl ether is important Organic Chemicals and chemical intermediate, can be used for the industries such as aerosol, cold-producing medium, alkylating agent, pharmacy, cosmetics, fuel.
Dimethyl ether, the earliest by obtained after the byproduct rectifying in high-pressure process methanol production, develops into methanol dehydration and synthesis gas directly synthesizes two kinds of techniques very soon.Liquid phase methanol dewatering preparing dimethy ether, reaction is carried out in the liquid phase, and major defect is that equipment corrosion is serious, operating condition severe, and environmental pollution is serious, and product post processing is more difficult to be eliminated gradually.And direct synthesis of dimethyl ether from synthesis gas still rests on the experimental study stage, the dominating process route producing dimethyl ether at present in the world remains vapor phase method methanol dehydration.
At present, the catalyst that methanol dehydration adopts is generally Al
2o
3or molecular sieve, wherein conventional molecular sieve has aluminum phosphate, HZSM-5, HY, SAPO etc., and they have respective shortcoming: although as high in aluminium oxide stability, reaction temperature is high, very high to the equipment requirement of reaction, causes high expensive; Molecular sieve catalysts acidity is comparatively strong, and initial temperature is low, but also there is the shortcoming of many, the easy carbon distributions of accessory substance, easy in inactivation.Because above catalyst also exists the shortcoming of self, make the preparation of dimethyl ether, investment is large, and cost is high, causes the production of dimethyl ether and use to be restricted.
CN00102506.6 discloses a kind of catalyst of preparing dimethyl ether by dewatering methanol.This catalyst take aluminium oxide as carrier, and the active component of load is heteropoly acid, and anti-carbon deposit component is titanium dioxide and lanthanum sesquioxide, adopts infusion process preparation.Wang Shouguo etc. [molecular science journal 2001,2 (17): 99-104] report and are entitled as H
4siW
12o
40-La
2o
3/ γ-Al
2o
3the article of catalysis methanol dehydration dimethyl ether-preparing, wherein catalyst is also adopt infusion process preparation.Above-mentioned catalyst has higher catalytic activity and selective in the reaction, the optimum load amount of silico-tungstic acid is 10wt% ~ 16wt%, at ambient pressure, during for the treatment of pure methanol feedstock, it is selective higher higher with activity, but during for moisture methanol feedstock, its stability is bad, selective and activity also declines thereupon.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of dimethyl ether by methanol dewater and preparation method thereof.When this catalyst is used for preparing dimethyl ether by dewatering methanol, low temperature active is high, selective good, good stability.
Described dimethyl ether by methanol dewater, comprises active component, auxiliary agent and carrier, and active component is that ammonium heteropoly acids is shown in formula (1), and auxiliary agent is lanthana and/or cerium oxide, and carrier is aluminium oxide; With the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 1% ~ 20%, and be preferably 5% ~ 18%, auxiliary agent is 1% ~ 10 %, Al with the content of oxide basis
2o
3content be 70 % ~ 98 %, be preferably 72% ~ 94%;
H
m(NH
4)
nYX
12O
40（1）
Wherein X represents W or Mo, and Y represents Si or P; When Y represents Si, m+n=4, n value is 0.05 ~ 1.0; When Y represents P, m+n=3, n value is 0.05 ~ 1.0.
The preparation method of described dimethyl ether by methanol dewater, comprising:
(1) presoma of auxiliary agent is joined containing in organic aqueous acid, obtain solution A;
(2) alumina support is joined in solution A, at 50 DEG C ~ 90 DEG C, be stirred to solution evaporate to dryness;
(3) solid that step (2) obtains is joined in the alkaline solution containing ammonium and flood, then filter, dry at 40 DEG C ~ 100 DEG C, or solid absorbing ammonia at 40 DEG C ~ 100 DEG C that step (2) is obtained;
(4) by the solid that step (3) obtains, join in the aqueous solution of heteropoly acid, at 50 DEG C ~ 90 DEG C, be stirred to solution evaporate to dryness;
(5) by the solid that step (4) obtains, drying, then at 300 DEG C ~ 550 DEG C roasting 2 h ~ 6 h, obtains catalyst.
In step (2), described alumina support is obtained through shaping, dry and roasting by boehmite.Described boehmite can adopt conventional method to obtain, such as: Alchlor process, aluminum sulfate method, carbonizatin method etc.Described roasting condition: sintering temperature is 400 DEG C ~ 700 DEG C, roasting time is 2 h ~ 10 h.
In step (1), described auxiliary agent presoma is one or more in lanthanum nitrate, cerous nitrate; Described organic acid can be in citric acid, tartaric acid, malic acid one or more, in described organic acid and step (2) alumina support used, the mol ratio of aluminium oxide is 0.05 ~ 0.5.
In step (3), joined by the solid that step (2) obtains in the alkaline solution containing ammonia and flood, dip time is generally 5 min ~ 30 min.By the solid absorption ammonia that step (2) obtains, adsorption time is generally 5 min ~ 30 min.
In step (3), the described alkaline solution containing ammonium is one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
In step (3), described ammonia can adopt pure ammonia, also can adopt the gaseous mixture containing ammonia, and in mist except ammonia, other is that inert gas is as one or more in nitrogen, argon gas etc.
In step (4), described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
In step (4), by the solid that step (3) obtains, join in the aqueous solution of heteropoly acid and flood, dip time is generally 5 min ~ 30 min.In step (4), be that solution is stirred to evaporate to dryness.
In step (5), described drying condition is as follows: 90 DEG C ~ 120 DEG C drying 5 h ~ 12 h.
Present invention also offers a kind of method of methanol dehydration dimethyl ether-preparing, wherein adopt catalyst of the present invention.Dimethyl ether by methanol dewater of the present invention is specially adapted to the higher methanol feedstock dewatering preparing dimethy ether reaction of water content.The water content of described methanol feedstock is 10wt% ~ 20wt%, can derive from the methyl alcohol that synthesis gas is obtained.In the present invention, the reaction condition of methanol dehydration dimethyl ether-preparing is as follows: reaction pressure 0 ~ 3.0 MPa, mass space velocity 0.5 h
-1~ 3.5 h
-1, reaction temperature 240 DEG C ~ 300 DEG C.
Compared with prior art, the present invention has the following advantages:
Carried heteropoly acid ammonium salt in catalysis of the present invention agent, can regulate the dispersion on carrier of auxiliary agent and ammonium heteropoly acids well, while making catalyst have higher activity, selective and coking resistivity, improves the stability of catalyst.During for the treatment of moisture higher methanol feedstock, still there is higher activity and selectivity.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
(1) catalyst preparing:
Take 8.0g lanthanum nitrate and 16.8g citric acid joins in deionized water, be made into mixed solution; 89g alumina support is joined in mixed solution, at 70 DEG C, is stirred to solution evaporate to dryness, wherein citric acid and Al
2o
3mol ratio be 0.1; Gained solid is put in sal volatile and floods 10min, dry at 60 DEG C after filtration; Gained solid is joined in the aqueous solution containing 8.3g phosphotungstic acid, at 70 DEG C, be stirred to solution evaporate to dryness, dry 8 h at 110 DEG C, roasting 3 h at 400 DEG C, obtained (NH
4)
0.7h
2.3pW
12o
40-La
2o
3/ Al
2o
3catalyst, wherein La
2o
3content is 3wt%, (NH
4)
0.7h
2.3pW
12o
40content is 8wt%.
(2) catalyst characterization:
Surrounding in catalyst granules cross section and centre are got a little, by SEM, elementary analysis is carried out to each point, result shows: promoter metal and the heteropoly acid ammonium salt content at each point place are substantially suitable, the catalyst adopting the method to prepare is described, the dispersion that its promoter metal and ammonium heteropoly acids have had on a catalyst.
(3) evaluation of catalyst:
The reaction of methyl alcohol (content 80wt%, water content 20wt%) dewatering preparing dimethy ether is carried out in fixed-bed tube reactor, normal pressure, mass space velocity 1.2h
-1, reaction temperature 260 DEG C.Before reaction, catalyst is at N
2in 400 DEG C of activation 2 h under protection, be then down to after reaction temperature starts to react 4 hours, product is analyzed by gas-chromatography, calculates selective and conversion ratio, the results are shown in Table 1.
Embodiment 2
Take 13.3g lanthanum nitrate and 31.3g citric acid joins in deionized water, be made into mixed solution; 83g alumina support is joined in mixed solution, at 70 DEG C, is stirred to solution evaporate to dryness, wherein citric acid and Al
2o
3mol ratio be 0.2; Gained solid is put in sal volatile and floods 10min, dry at 60 DEG C after filtration; Gained solid is joined in the aqueous solution containing 12.5g phosphotungstic acid, at 70 DEG C, be stirred to solution evaporate to dryness, dry 8 h at 110 DEG C, roasting 3 h at 470 DEG C, obtained (NH
4)
0.5h
2.5pW
12o
40-La
2o
3/ Al
2o
3catalyst, wherein La
2o
3content is 5wt%, (NH
4)
0.5h
2.5pW
12o
40content is 12wt%.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 1.
Embodiment 3
Take 21.3g lanthanum nitrate and 43.5g citric acid joins in deionized water, be made into mixed solution; 77g alumina support is joined in mixed solution, at 70 DEG C, is stirred to solution evaporate to dryness, wherein citric acid and Al
2o
3mol ratio be 0.3; Gained solid is put in sal volatile and floods 10min, dry at 60 DEG C after filtration; Gained solid is joined in the aqueous solution containing 15.6g phosphotungstic acid, at 70 DEG C, be stirred to solution evaporate to dryness, dry 8 h at 110 DEG C, roasting 3 h at 500 DEG C, obtained (NH
4)
0.1h
2.9pW
12o
40-La
2o
3/ Al
2o
3catalyst, wherein La
2o
3content is 8wt%, (NH
4)
0.1h
2.9pW
12o
40content is 15wt%.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 1.
Embodiment 4
In embodiment 3, lanthanum nitrate is changed into 20.2g cerous nitrate, citric acid changes 58g into, citric acid and Al
2o
3mol ratio be 0.4, all the other are with embodiment 3, and gained catalyst is (NH
4)
0.1h
2.9pW
12o
40-CeO
2/ Al
2o
3, wherein CeO
2content is 8wt%, (NH
4)
0.1h
2.9pW
12o
40content is 15wt%.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 1.
Embodiment 5
In embodiment 3, change phosphotungstic acid into silico-tungstic acid, citric acid changes 34.0g tartaric acid into, tartaric acid and Al
2o
3mol ratio be 0.3, all the other are with embodiment 3, and gained catalyst is (NH
4)
0.1h
3.9siW
12o
40-La
2o
3/ Al
2o
3, wherein La
2o
3content is 8wt%, (NH
4)
0.1h
3.9siW
12o
40content is 15wt%.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 1.
Embodiment 6
Obtain catalyst according to embodiment 3, and test the estimation of stability that catalyst has carried out 100 h according to the appreciation condition of embodiment 3, conversion ratio and the selective of crackate the results are shown in Table 2.
Comparative example 1
Take 13.3g lanthanum nitrate and 15.6g phosphotungstic acid joins in deionized water, be made into mixed solution; 80g alumina support is joined in mixed solution, at 70 DEG C, is stirred to solution evaporate to dryness; Dry 8 h at 110 DEG C, roasting 3 h at 350 DEG C, obtained H
3pW
12o
40-La
2o
3/ Al
2o
3catalyst, wherein La
2o
3content is 5wt%, H
3pW
12o
40content is 15wt%.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 1.
Comparative example 2
Obtain catalyst according to comparative example 1, the appreciation condition according to embodiment 3 is tested the estimation of stability that catalyst has carried out 100 h, and conversion ratio and the selective of crackate the results are shown in Table 2.
The conversion ratio of each routine catalyst of table 1 and selective
Table 2 stability test evaluation result
| Embodiment | Conversion ratio, wt% | Selective, wt% |
| Embodiment 6 | 78.2 | 97.9 |
| Comparative example 2 | 45.3 | 86.1 |
Claims (15)
1. a dimethyl ether by methanol dewater, comprises active component, auxiliary agent and carrier, and active component is that ammonium heteropoly acids is shown in formula (1), and auxiliary agent is lanthana and/or cerium oxide, and carrier is aluminium oxide; With the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 1% ~ 20%, and auxiliary agent is 1% ~ 10 %, Al with the content of oxide basis
2o
3content be 70 % ~ 98 %;
H
m(NH
4)
nYX
12O
40（1）
Wherein X represents W or Mo, and Y represents Si or P; When Y represents Si, m+n=4, n value is 0.05 ~ 1.0; When Y represents P, m+n=3, n value is 0.05 ~ 1.0.
2. in accordance with the method for claim 2, it is characterized in that: with the weight of catalyst for benchmark, the content of ammonium heteropoly acids is 5% ~ 18%, and auxiliary agent is 1% ~ 10 %, Al with the content of oxide basis
2o
3content be 72% ~ 94%.
3. the preparation method of catalyst described in claim 1 or 2, comprising:
(1) presoma of auxiliary agent is joined containing in organic aqueous acid, obtain solution A;
(2) alumina support is joined in solution A, at 50 DEG C ~ 90 DEG C, be stirred to solution evaporate to dryness;
(3) solid that step (2) obtains is joined in the alkaline solution containing ammonium and flood, then filter, dry at 40 DEG C ~ 100 DEG C, or solid absorbing ammonia at 40 DEG C ~ 100 DEG C that step (2) is obtained;
(4) by the solid that step (3) obtains, join in the aqueous solution of heteropoly acid, at 50 DEG C ~ 90 DEG C, be stirred to solution evaporate to dryness;
(5) by the solid that step (4) obtains, drying, then at 300 DEG C ~ 550 DEG C roasting 2 h ~ 6 h, obtains catalyst.
4. in accordance with the method for claim 3, it is characterized in that: in step (2), described alumina support is obtained, described roasting condition through shaping, dry and roasting by boehmite: sintering temperature is 400 DEG C ~ 700 DEG C, and roasting time is 2 h ~ 10 h.
5. in accordance with the method for claim 3, it is characterized in that: in step (1), described auxiliary agent presoma is one or more in lanthanum nitrate, cerous nitrate.
6. in accordance with the method for claim 3, it is characterized in that: in step (1), described organic acid is one or more in citric acid, tartaric acid, malic acid.
7. in accordance with the method for claim 3, it is characterized in that: in step (1), in described organic acid and step (2) alumina support used, the mol ratio of aluminium oxide is 0.05 ~ 0.5.
8. in accordance with the method for claim 3, it is characterized in that: in step (3), joined by the solid that step (2) obtains in the alkaline solution containing ammonia and flood, dip time is 5 min ~ 30 min; By the solid absorption ammonia that step (2) obtains, adsorption time is 5 min ~ 30 min.
9. in accordance with the method for claim 3, it is characterized in that: in step (3), the described alkaline solution containing ammonium is one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
10. in accordance with the method for claim 3, it is characterized in that: in step (3), described ammonia adopts pure ammonia or adopts the gaseous mixture containing ammonia, and in mist except ammonia, other is one or more in inert nitrogen gas, argon gas.
11. in accordance with the method for claim 3, it is characterized in that: in step (4), and described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
12. in accordance with the method for claim 3, it is characterized in that: in step (5), described drying condition is as follows: 90 DEG C ~ 120 DEG C drying 5 h ~ 12 h.
The method of 13. 1 kinds of methanol dehydration dimethyl ether-preparings, is characterized in that the catalyst adopting claim 1 or 2 to prepare.
14. in accordance with the method for claim 13, it is characterized in that in described methanol feedstock, water content is 10wt% ~ 20wt%.
15., according to the method described in claim 13 or 14, is characterized in that: the reaction condition of methanol dehydration dimethyl ether-preparing is as follows: reaction pressure 0 ~ 3.0 MPa, mass space velocity 0.5 h
-1~ 3.5 h
-1, reaction temperature 240 DEG C ~ 300 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019037766A1 (en) | 2017-08-24 | 2019-02-28 | Bp P.L.C. | Process |
| US11673851B2 (en) | 2017-08-24 | 2023-06-13 | Bp P.L.C. | Process for dehydrating methanol to dimethyl ether product |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173394A (en) * | 1997-02-27 | 1998-02-18 | 大连理工大学 | Prepn. and application of heteropolyacid salt modified skeletal nickel catalyst |
| CN1285240A (en) * | 1999-08-23 | 2001-02-28 | 罗姆和哈斯公司 | Multi-metal axide supported catalyst |
| CN1541991A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Hydrolysis method of esters |
| CN1793099A (en) * | 2005-12-28 | 2006-06-28 | 浙江工业大学 | Process for preparing cyclohexone by catalyzing oxidating cyclohexol |
| US20070021629A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
| CN101538203A (en) * | 2009-04-08 | 2009-09-23 | 聊城大学 | Method for catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium |
| CN101641156A (en) * | 2007-06-13 | 2010-02-03 | Lg化学株式会社 | The method for preparing heteropolyacid catalyst |
-
2013
- 2013-11-03 CN CN201310532029.XA patent/CN104588060B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173394A (en) * | 1997-02-27 | 1998-02-18 | 大连理工大学 | Prepn. and application of heteropolyacid salt modified skeletal nickel catalyst |
| CN1285240A (en) * | 1999-08-23 | 2001-02-28 | 罗姆和哈斯公司 | Multi-metal axide supported catalyst |
| CN1541991A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Hydrolysis method of esters |
| US20070021629A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
| CN1793099A (en) * | 2005-12-28 | 2006-06-28 | 浙江工业大学 | Process for preparing cyclohexone by catalyzing oxidating cyclohexol |
| CN101641156A (en) * | 2007-06-13 | 2010-02-03 | Lg化学株式会社 | The method for preparing heteropolyacid catalyst |
| CN101538203A (en) * | 2009-04-08 | 2009-09-23 | 聊城大学 | Method for catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium |
Non-Patent Citations (3)
| Title |
|---|
| B.Y. GIRI,ET AL: "Esterification of palmitic acid on the ammonium salt of 12-tungstophosphoric acid: The influence of partial proton exchange on the activity of the catalyst", 《CATALYSIS COMMUNICATIONS》 * |
| B.Y. GIRI,ET AL: "Esterification of palmitic acid on the ammonium salt of 12-tungstophosphoric acid: The influence of partial proton exchange on the activity of the catalyst", 《CATALYSIS COMMUNICATIONS》, vol. 6, no. 12, 19 September 2005 (2005-09-19), pages 788 - 792 * |
| 王守国等: "H4SiW12O40-La2O3/γ-Al2O3催化甲醇脱水制备二甲醚", 《分子科学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019037766A1 (en) | 2017-08-24 | 2019-02-28 | Bp P.L.C. | Process |
| US11427524B2 (en) | 2017-08-24 | 2022-08-30 | Bp P.L.C. | Process for dehydrating methanol to dimethyl ether product |
| US11673851B2 (en) | 2017-08-24 | 2023-06-13 | Bp P.L.C. | Process for dehydrating methanol to dimethyl ether product |
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|---|---|
| CN104588060B (en) | 2017-01-04 |
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