CN101940940B - Catalyst for oxidizing and converting methanol - Google Patents
Catalyst for oxidizing and converting methanol Download PDFInfo
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- CN101940940B CN101940940B CN2009101578573A CN200910157857A CN101940940B CN 101940940 B CN101940940 B CN 101940940B CN 2009101578573 A CN2009101578573 A CN 2009101578573A CN 200910157857 A CN200910157857 A CN 200910157857A CN 101940940 B CN101940940 B CN 101940940B
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Abstract
The invention discloses a catalyst for oxidizing and converting methanol, which comprises at least one molecular sieve with acid catalytic activity, and metal components molybdenum and iron, wherein the molecular sieve accounts for 40 to 95 weight percent of the catalyst, and the metal component molybdenum accounts for 0.5 to 50 weight percent and the metal component iron accounts for 0.2 to 20 weight percent based on oxides. Compared with the prior art, the catalyst provided by the invention can directly convert the methanol into dimethyl ether and polymethoxy dimethyl ether (DMMX, wherein x is more than or equal to 2 and less than or equal to 8) through one-step reaction. The reaction product is simply separated to prepare the polymethoxy dimethyl ether (DMMX, wherein x is more than or equal to 2 and less than or equal to 8), and the catalyst is particularly suitable for producing the polymethoxy dimethyl ether (DMMX, wherein x is more than or equal to 2 and less than or equal to 8) from the methanol serving as a raw material.
Description
Technical field
The present invention relates to a kind of methanol conversion catalyst, more specifically to a kind of catalyst by oxidation conversion methyl alcohol.
Background technology
Produce all kinds of useful chemicals take methyl alcohol as raw material, be the importance of C1 technical research always.
For example, in the presence of catalyst, the methanol dehydration dimethyl ether synthesis.Dimethyl ether has good combustion characteristics, and Cetane number is high, can be widely used in civil LPG substitute and onboard fuel.In addition, dimethyl ether can also be as uses such as the propellant of aerosol, blowing agent, solvent, extractants.
US6166266 discloses a kind of with formaldehyde with contain the raw material of dimethyl ether, and the ion exchange resin of making catalyst or having Bronsted acid take the borosilicate with MFI structure is as catalyst, synthetic polymethoxy dimethyl ether (CH
3O (CH
2O)
xCH
3, be abbreviated as DMM
X, 2≤x≤8) method.
EP1505049A1 discloses and has a kind ofly utilized fluosulfonic acid to be catalyst take dimethoxym ethane and polyformaldehyde as raw material, the method for synthetic polymethoxy dimethyl ether (DMMx, 2≤x≤5).
Polymethoxy dimethyl ether (DMM
X) have equally higher Cetane number (＞60), can be used as compression-ignited diesel motor fuel or diesel fuel additives and use.In addition, polymethoxy dimethyl ether (DMM
X) be liquid under the normal temperature, the accumulating of being more convenient for.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of catalyst of new oxidation conversion methyl alcohol.
The invention provides a kind of catalyst of oxidation conversion methyl alcohol, described catalyst contains at least a molecular sieve and metal component molybdenum and iron with surface acidity, take catalyst as benchmark, the content of described molecular sieve is 40～95 % by weight, in oxide, the content of described metal component molybdenum is 0.5～50 % by weight, and the content of ferrous metal component is 0.2～20 % by weight.
According to catalyst provided by the invention, wherein, the metal component molybdenum in the described catalyst and iron can be to exist with different shapes such as their corresponding salt, oxide or sulfide, and preferably the oxide with them exists.In oxide and take catalyst as benchmark, the content of the metal component of described group vib is preferably 2～20 % by weight, and the metal component content of group VIII is preferably 0.2～10 % by weight.
Described molecular sieve with surface acidity is one or more in the molecular sieve with central hole structure and/or macroporous structure preferably, preferred mesoporous molecular sieve is ZSM-5, molecular sieve with macroporous structure is Y zeolite, one or more among HY, the REY in the further preferred Y zeolite, REHY, USY, the REUSY.Take catalyst as benchmark, the content of described molecular sieve is preferably 70 % by weight～90 % by weight.
Described molecular sieve can be commercially available commodity, also can adopt any existing method preparation.For example, CN1187462A, CN1121979C, CN1257840C philosophy openly have ZSM-5 molecular sieve and the synthetic method thereof of Different Silicon aluminum ratio, different crystal grain and phosphorous or rare earth; CN1005387B, CN1069553C, CN1205915A, CN10610976A philosophy disclose molecular sieve and the synthetic method thereof of HY, REY, REHY, USY, REUSY.Here quote as a reference in the lump.
Be enough to make described metal component to be carried under the condition on the described molecular sieve, the present invention is not particularly limited the preparation method of described catalyst.For example, can at first the compound that contains described metal component be mixed with the aqueous solution, again with the described molecular sieve with surface acidity of this solution impregnation, the afterwards method of drying, roasting or not roasting preparation.The method of described drying and roasting and condition are Kaolinite Preparation of Catalyst customary way and condition.Preferred drying condition comprises: 50～300 ℃ of temperature, 0.5～12 hour time, 100～250 ℃ of further preferred temperature, 1～6 hour time; Preferred roasting condition comprises: 350～650 ℃ of temperature, 0.5～12 hour drying time, 400～600 ℃ of further preferred temperature, 1～4 hour time.
According to catalyst provided by the invention, wherein said catalyst can be the article shaped of various easy operatings, such as microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, and the method for compressing tablet, extrusion or roller forming.When described catalyst was the article shaped of various easy operatings, described moulding can be at first with described molecular sieve molded, afterwards the carried metal component; Also can be first described molecular sieve to be mixed with described metal component, reshaping afterwards.
Described moulding adopts customary way to carry out, and all can such as methods such as compressing tablet, spin, extrusions.When adopting the customary way moulding, for guarantee moulding carry out smoothly in described mixture, introduce auxiliary agent and allow, for example when extrusion, can be to an amount of extrusion aid of introducing and water, afterwards extrusion molding in the mixture.The kind of described extrusion aid and consumption all can be this area routines, and for example common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, the PVOH.
According to catalyst provided by the invention, wherein, preferably also contain heat-resistant inorganic oxide matrix in the described catalyst, take catalyst as benchmark, the content of described heat-resistant inorganic oxide matrix is no more than 80 % by weight, preferably is no more than 60 % by weight, further preferentially less than 25 % by weight.
Described heat-resistant inorganic oxide matrix is the heat-resistant inorganic oxide of Chang Zuowei catalyst support substrate.For example, be selected from aluminium oxide, silica, titanium oxide, magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, silica-zirconia, oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, the silica-alumina-zirconia one or more.In the preferred aluminium oxide, silica, silica-alumina wherein one or more.
When also containing heat-resistant inorganic oxide matrix in the described catalyst, be enough to guarantee that described metal component is carried under the condition on the mixture of described molecular sieve and described heat-resistant inorganic oxide matrix, the present invention is not particularly limited the preparation method of described catalyst.
Preferred preparation method comprises:
(1) described molecular sieve is mixed with the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix;
The compound that (2) will contain described metal component is mixed with the aqueous solution;
(3) mixture that obtains with the solution impregnation step (1) of step (2), the method preparation of afterwards dry, roasting or not roasting;
The method of described drying and roasting and condition are conventional process and condition.Preferred drying condition comprises: 50～300 ℃ of temperature, 0.5～12 hour time, 10～200 ℃ of further preferred temperature, 1～6 hour time; Preferred roasting condition comprises: 350～600 ℃ of temperature, 0.5～8 hour drying time, 400～500 ℃ of further preferred temperature, 1～4 hour time.
When the precursor that adopts described heat-resistant inorganic oxide matrix and described molecular sieve are mixed with catalyst, described mixing after, preferably include the step of a roasting, the method for described roasting and condition are method and the condition of the catalyst of habitually practising in preparing.Preferred drying condition comprises: 50～300 ℃ of temperature, 0.5～12 hour time, 10～200 ℃ of further preferred temperature, 1～6 hour time; Preferred roasting condition comprises: 350～600 ℃ of temperature, 0.5～8 hour drying time, 400～500 ℃ of further preferred temperature, 1～4 hour time.
According to catalyst provided by the invention, in described catalyst, also contain heat-resistant inorganic oxide matrix, the more preferential article shaped that described catalyst be can be made into various easy operatings, such as microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, and the method for compressing tablet, extrusion or roller forming.Although when described catalyst was the article shaped of various easy operatings, described moulding can be at first with described molecular sieve, heat-resistant inorganic oxide mixed-forming, afterwards carried metal component; Also can be first described molecular sieve to be mixed with described metal component, afterwards again with the heat-resistant inorganic oxide mixed-forming.One preferred embodiment in, preferably with described molecular sieve with carry out moulding after the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is mixed.When adopting the customary way moulding, for guarantee moulding carry out smoothly in described mixture, introduce auxiliary agent and allow, for example when extrusion, can be to an amount of extrusion aid of introducing and water, afterwards extrusion molding in the mixture.The kind of described extrusion aid and consumption all can be this area routines, and for example common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, the PVOH.
Compared with prior art, catalyst provided by the invention can directly be dimethyl ether and polymethoxy dimethyl ether (DMM with methanol conversion through single step reaction
X, 2≤x≤8).This product just obtains polymethoxy dimethyl ether (DMM through simple separation
X, 2≤x≤8), be particularly suitable for the production polymethoxy dimethyl ether (DMM take methyl alcohol as raw material
X, 2≤x≤8).
The specific embodiment
Further specify the present invention below by example, but the present invention is not limited to this.
The suitable Catalysts and its preparation method provided by the invention of embodiment 1～7 explanation.
Example 1
51g ammonium molybdate and 5g ferric nitrate are dissolved in the 3L deionized water, under agitation use this solution impregnation 700gZSM-5 molecular sieve (SiO
2/ Al
2O
3(mol ratio) is 30, Chang Ling catalyst plant product) 5 hours, afterwards, after filtration, in 200 ℃ of dryings 2 hours, 500 ℃ of roastings obtained catalyst C1 in 1 hour.The composition of catalyst C1 is listed in (wherein, the content of metal component adopts the X-fluorescence method to measure, and is lower same) in the table 1.
Example 2
51g ammonium molybdate and 5g ferric nitrate are dissolved in the 3L deionized water, add 700g ZSM-5 molecular sieve (SiO after the dissolving
2/ Al
2O
3(mol ratio) is 50, Chang Ling catalyst plant product), 5 hours, afterwards, after filtration, in 200 ℃ of dryings 2 hours, 500 ℃ of roastings obtained catalyst C2 in 1 hour.The composition of catalyst C2 is listed in the table 1.
Example 3
102g ammonium molybdate and 10g ferric nitrate are dissolved in the 3L deionized water, add 700g ZSM-5 molecular sieve (SiO after the dissolving
2/ Al
2O
3(mol ratio) is 80, Chang Ling catalyst plant product), 5 hours, afterwards, after filtration, in 200 ℃ of dryings 2 hours, 500 ℃ of roastings obtained catalyst C3 in 1 hour.The composition of catalyst C3 is listed in the table 1.
Example 4
51g ammonium molybdate and 5g ferric nitrate are dissolved in the 3L deionized water, add 700g USY molecular sieve (Chang Ling catalyst plant product) after the dissolving, 5 hours, afterwards, after filtration, in 200 ℃ of dryings 2 hours, 500 ℃ of roastings obtained catalyst C4 in 1 hour.The composition of catalyst C4 is listed in the table 1.
Example 5
51g ammonium molybdate and 5g ferric nitrate are dissolved in the 3L deionized water, add 700g REY molecular sieve (rare earth mass content 6%, Chang Ling catalyst plant product) after the dissolving, 5 hours, afterwards, after filtration, in 200 ℃ of dryings 2 hours, 500 ℃ of roastings obtained catalyst C5 in 1 hour.The composition of catalyst C5 is listed in the table 1.
Example 6
51g ammonium molybdate and 5g ferric nitrate are dissolved in the 3L deionized water, add 700g REY molecular sieve (rare earth mass content 12%, Chang Ling catalyst plant product) after the dissolving, under 30 ℃, stirred 5 hours; Then catalyst is placed 200 ℃ of baking ovens dry 2 hours, and obtained catalyst 6.The composition of catalyst C6 is listed in the table 1.
Example 7
51g ammonium molybdate and 5g ferric nitrate are dissolved in the 3L deionized water, add 700gHY molecular sieve (Chang Ling catalyst plant product) after the dissolving, 5 hours, afterwards, after filtration, in 200 ℃ of dryings 2 hours, 500 ℃ of roastings obtained catalyst C7 in 1 hour.The composition of catalyst C7 is listed in the table 1.
Example 8
With the Al of 700g REY molecular sieve (rare earth mass content 6%,, Chang Ling catalyst plant product) with weight percent meter 10%
2O
3Mix, adopts 1.2 millimeters column type orifice plate extruded moulding, wet bar was dried 3 hours at 120 ℃, 500 ℃ of lower roastings 2 hours.After being down to room temperature, this carrier is contained 51g ammonium molybdate and 5g iron nitrate aqueous solution dipping 5 hours with 3L, afterwards, after filtration, in 200 ℃ of dryings 2 hours, 500 ℃ of roastings obtained catalyst C8 in 1 hour.The composition of catalyst C8 is listed in the table 1.
Example 9
With the SiO of 700g REY molecular sieve (rare earth mass content 6%) with weight percent meter 30%
2-Al
2O
3Mix, 51g ammonium molybdate and 5g ferric nitrate are dissolved in the 3L deionized water dissolve, with molecular sieve SiO
2-Al
2O
3Mixture add in the deionized water solution, 5 hours, afterwards, after filtration, in 200 ℃ of dryings 2 hours, 500 ℃ of roastings obtained catalyst C9 in 1 hour.The composition of catalyst C9 is listed in the table 1.
Example 10
102g ammonium molybdate and 10g ferric nitrate are dissolved in the 3L deionized water, add 700g REY molecular sieve (rare earth mass content 6%, Chang Ling catalyst plant product) after the dissolving, under 30 ℃, stirred 5 hours; Then catalyst is placed 200 ℃ of baking ovens dry 2 hours, and obtained catalyst 10.The composition of catalyst C10 is listed in the table 1.
Table 1
| Embodiment | Catalyst | Molecular sieve, % | Matrix, % | Molybdenum oxide, % | Iron oxide, % |
| 1 | C1 | 89.32 | 0 | 8.27 | 2.41 |
| 2 | C2 | 86.48 | 0 | 8.40 | 5.12 |
| 3 | C3 | 74.89 | 0 | 16.17 | 8.94 |
| 4 | C4 | 90.18 | 0 | 8.36 | 1.46 |
| 5 | C5 | 90.71 | 0 | 8.67 | 0.62 |
| 6 | C6 | 91.83 | 0 | 7.61 | 0.56 |
| 7 | C7 | 95.08 | 0 | 4.57 | 0.35 |
| 8 | C8 | 83.60 | 8.36 | 7.62 | 0.42 |
| 9 | C9 | 71.16 | 21.35 | 7.12 | 0.37 |
| 10 | C10 | 75.42 | 0 | 17.06 | 7.52 |
Example 11～20 explanations the invention provides the performance of catalyst.
Reaction is carried out in fixed bed reactors, and material benzenemethanol is the analysis net product of Beijing Chemical Plant, and oxygen-containing gas is air.Wherein, catalyst C1～C7, C10 through compressing tablet, fragmentation, be screened into 20～40 purpose particles, bar shaped catalyst C8～C9 through broken, be screened into 20～40 purpose particles.
Each embodiment lists in table 2 with catalyst and reaction condition.
React sample analysis after 2 hours.Sample analysis carries out in Agilent 6890 chromatograms.
Methanol conversion=((MOH
Before the reaction-MOH
After the reaction)/MOH
Before the reaction) * 100%
Polymethoxy dimethyl ether is selective=(DMM
X/ (MOH
Before the reaction-MOH
After the reaction)) * 100%
The results are shown in table 3.
Comparative Examples 1～2
Example 1 and example 6 molecular sieves respectively through compressing tablet, fragmentation, be screened into 20～40 purpose particles, and adopt example 11 reaction conditions to estimate, the results are shown in table 3.
Table 2
| Embodiment | Catalyst | Temperature, ℃ | Pressure, MPa | Air speed, h -1 | Oxygen/methyl alcohol |
| 11 | C1 | 200 | 0.2 | 5 | 0.05 |
| 12 | C2 | 250 | 0.3 | 13 | 0.30 |
| 13 | C3 | 300 | 0.6 | 13 | 0.20 |
| 14 | C4 | 150 | 0.3 | 10 | 0.15 |
| 15 | C5 | 250 | 1.1 | 13 | 0.20 |
| 16 | C6 | 250 | 1.6 | 13 | 0.30 |
| 17 | C7 | 350 | 0.3 | 20 | 0.10 |
| 18 | C8 | 250 | 1.6 | 13 | 0.10 |
| 19 | C9 | 300 | 1.1 | 13 | 0.10 |
| 20 | C10 | 250 | 1.1 | 13 | 0.20 |
Table 3
| Embodiment | Catalyst | Methanol conversion/% | DMMx is selective/% |
| 11 | C1 | 61.5 | 3.6 |
| 12 | C2 | 83.4 | 7.1 |
| 13 | C3 | 90.6 | 4.2 |
| 14 | C4 | 81.4 | 15.9 |
| 15 | C5 | 97.2 | 26.4 |
| 16 | C6 | 98.4 | 34.1 |
| 17 | C7 | 87.1 | 10.9 |
| 18 | C8 | 94.1 | 21.4 |
| 19 | C9 | 89.2 | 17.2 |
| 20 | C10 | 97.4 | 27.9 |
| Comparative Examples 1 | ZSM-5 | 60.9 | 0 |
| Comparative Examples 2 | REY | 94.7 | 5.1 |
Compare with reference method, method provided by the invention can directly be dimethyl ether and polymethoxy dimethyl ether (DMM with methanol conversion through single step reaction
X, 2≤x≤8), particularly such as embodiment 16, when the molecular sieve that adopts in the described catalyst was the REY molecular sieve, the conversion ratio of methyl alcohol can selectively reach 34.1% up to 98.4%, DMMx, is particularly suitable for requiring to have the production process of higher DMMx yield.
Claims (8)
1. the catalyst of an oxidation conversion methyl alcohol, described catalyst contains at least a molecular sieve and metal component molybdenum and iron with surface acidity, take catalyst as benchmark, the content of described molecular sieve is 40～95 % by weight, in oxide, the content of described metal component molybdenum is 0.5～50 % by weight, and the content of ferrous metal component is 0.2～20 % by weight, described one or more in the molecular sieve with macroporous structure of molecular screening with surface acidity.
2. catalyst according to claim 1 is characterized in that, take catalyst as benchmark, the content of described molecular sieve is 70～90 % by weight, in oxide, the content of described metal component molybdenum is 2～20 % by weight, and the content of metal component iron is 0.2～10 % by weight.
3. method according to claim 1 and 2 is characterized in that, described have the molecular screening of macroporous structure from Y zeolite.
4. catalyst according to claim 3 is characterized in that, described Y zeolite is selected from one or more among HY, REY, REHY, USY, the REUSY.
5. catalyst according to claim 4 is characterized in that, described Y zeolite is selected from one or more among REY, REHY, the REUSY.
6. catalyst according to claim 1 is characterized in that, contains heat-resistant inorganic oxide matrix in the described catalyst, and take catalyst as benchmark, the content of described heat-resistant inorganic oxide matrix is less than 80 % by weight.
7. catalyst according to claim 6, it is characterized in that, described heat-resistant inorganic oxide matrix is selected from one or more in aluminium oxide, silica, the silica-alumina, and take catalyst as benchmark, the content of described heat-resistant inorganic oxide matrix is less than 60 % by weight.
8. catalyst according to claim 7 is characterized in that, described heat-resistant inorganic oxide matrix is selected from aluminium oxide, and take catalyst as benchmark, the content of described heat-resistant inorganic oxide matrix is less than 25 % by weight.
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|---|---|---|---|
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|---|---|---|---|
| CN2009101578573A CN101940940B (en) | 2009-07-09 | 2009-07-09 | Catalyst for oxidizing and converting methanol |
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| CN102030621B (en) * | 2009-09-29 | 2014-07-30 | 中国石油化工股份有限公司 | Process for generating DMMx from methanol by gas phase method |
| CN108212197B (en) * | 2018-01-23 | 2019-12-10 | 西南化工研究设计院有限公司 | Catalyst for preparing polymethoxy dimethyl ether from dimethyl ether and preparation and application thereof |
Citations (4)
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|---|---|---|---|---|
| CN1065028A (en) * | 1991-03-20 | 1992-10-07 | 中国科学院大连化学物理研究所 | Process for preparing low carbon alkene by catalytic conversion of light hydrocarbon |
| CN1401412A (en) * | 2002-09-28 | 2003-03-12 | 太原理工大学 | Nitrogen oxide purifying catalyst and preparation thereof |
| CN101322945A (en) * | 2008-08-01 | 2008-12-17 | 中国海洋石油总公司 | Method for preparing sulphur-containing condensate oil modifying catalyst and use |
| CN101451074A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Catalyst for heavy oil catalytic cracking and preparation method thereof |
-
2009
- 2009-07-09 CN CN2009101578573A patent/CN101940940B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065028A (en) * | 1991-03-20 | 1992-10-07 | 中国科学院大连化学物理研究所 | Process for preparing low carbon alkene by catalytic conversion of light hydrocarbon |
| CN1401412A (en) * | 2002-09-28 | 2003-03-12 | 太原理工大学 | Nitrogen oxide purifying catalyst and preparation thereof |
| CN101451074A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Catalyst for heavy oil catalytic cracking and preparation method thereof |
| CN101322945A (en) * | 2008-08-01 | 2008-12-17 | 中国海洋石油总公司 | Method for preparing sulphur-containing condensate oil modifying catalyst and use |
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