CN101940940A - Catalyst for oxidizing and converting methanol - Google Patents

Catalyst for oxidizing and converting methanol Download PDF

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Publication number
CN101940940A
CN101940940A CN2009101578573A CN200910157857A CN101940940A CN 101940940 A CN101940940 A CN 101940940A CN 2009101578573 A CN2009101578573 A CN 2009101578573A CN 200910157857 A CN200910157857 A CN 200910157857A CN 101940940 A CN101940940 A CN 101940940A
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catalyst
molecular sieve
weight
content
metal component
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CN101940940B (en
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于鹏
荣峻峰
付强
张巍
周旭华
毛国芳
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/50—Improvements relating to the production of bulk chemicals

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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

A kind of catalyst of oxidation conversion methyl alcohol
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
With methyl alcohol is that raw material is produced all kinds of useful chemicals, is 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 the Cetane number height 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 a Bronsted acid with the borosilicate with MFI structure is catalyst, synthetic polymethoxy dimethyl ether (CH 3O (CH 2O) xCH 3, be abbreviated as DMM X, 2≤x≤8) method.
It is raw material with dimethoxym ethane and polyformaldehyde that EP1505049A1 discloses a kind of, utilizes fluosulfonic acid to be catalyst, the method for synthetic polymethoxy dimethyl ether (DMMx, 2≤x≤5).
Polymethoxy dimethyl ether (DMM X) have higher Cetane number (＞60) equally, can be used as compression-ignited diesel motor fuel or diesel fuel additives and use.In addition, polymethoxy dimethyl ether (DMM X) normal temperature is down liquid, 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 acid catalysis activity, with the catalyst is benchmark, the content of described molecular sieve is 40～95 weight %, in oxide, the content of described metal component molybdenum is 0.5～50 weight %, and the ferrous metal components contents is 0.2～20 weight %.
According to catalyst provided by the invention, wherein, 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 with the catalyst is benchmark, and the content of the metal component of described group vib is preferably 2～20 weight %, and the metal component content of group VIII is preferably 0.2～10 weight %.
Described molecular sieve with acid catalysis activity 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 a Y zeolite, one or more among HY, the REY in the further preferred Y zeolite, REHY, USY, the REUSY.With the catalyst is benchmark, and the content of described molecular sieve is preferably 70 weight %～90 weight %.
Described molecular sieve can be commercially available commodity, also can adopt any existing method preparation.For example, CN1187462A, CN1121979C, CN1257840C etc. openly have the ZSM-5 molecular sieve and the synthetic method thereof of Different Silicon aluminum ratio, different crystal grain and phosphorous or rare earth respectively; CN1005387B, CN1069553C, CN1205915A, CN10610976A etc. disclose molecular sieve and the synthetic method thereof of HY, REY, REHY, USY, REUSY respectively.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 described Preparation of catalysts method.For example, can at first the compound that contains described metal component be mixed with the aqueous solution, again with the described molecular sieve of this solution impregnation with acid catalysis activity, the method for drying, roasting or not roasting preparation afterwards.The method of described drying and roasting and condition are preparation 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, for example 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 earlier described molecular sieve to be mixed with described metal component, reshaping afterwards.
Described moulding adopts customary way to carry out, and all can 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 in mixture, introduce an amount of extrusion aid and water, extrusion molding afterwards.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 poly-ethanol.
According to catalyst provided by the invention, wherein, preferably also contain heat-resistant inorganic oxide matrix in the described catalyst, with the catalyst is benchmark, the content of described heat-resistant inorganic oxide matrix is no more than 80 weight %, preferably is no more than 60 weight %, further preferentially less than 25 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 described Preparation of catalysts method.
Preferred manufacturing procedure comprises:
(1) described molecular sieve is mixed with the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix;
(2) compound that 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 dry afterwards, 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 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 in the Preparation of Catalyst of habitually practising.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, more preferential described catalyst be can be made into the article shaped of various easy operatings, for example 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.Though 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, carried metal component afterwards; Also can be earlier 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 in mixture, introduce an amount of extrusion aid and water, extrusion molding afterwards.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 poly-ethanol.
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), being particularly suitable for methyl alcohol is that raw material is produced polymethoxy dimethyl ether (DMM 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 spectrometry, down together) in the table 1.
Example 2
51g ammonium molybdate and 5g ferric nitrate are dissolved in the 3L deionized water, and the dissolving back adds 700g ZSM-5 molecular sieve (SiO 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, and the dissolving back adds 700g ZSM-5 molecular sieve (SiO 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, and dissolving back adds 700g USY molecular sieve (Chang Ling catalyst plant product), and 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, and the dissolving back adds 700g REY molecular sieve (rare earth mass content 6%, Chang Ling catalyst plant product), 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, and the dissolving back adds 700g REY molecular sieve (rare earth mass content 12%, Chang Ling catalyst plant product), under 30 ℃, stirs 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, and dissolving back adds 700gHY molecular sieve (Chang Ling catalyst plant product), and 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 following roastings 2 hours.After reducing 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, 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, and the dissolving back adds 700g REY molecular sieve (rare earth mass content 6%, Chang Ling catalyst plant product), under 30 ℃, stirs 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.
Be reflected in the fixed bed reactors and carry out, material benzenemethanol is the analysis net product of Beijing Chemical Plant, and oxygen-containing gas is an 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 selectivity=(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 selectivity/%
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 the 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 as embodiment 16, when the molecular sieve that is adopted in the described catalyst was the REY molecular sieve, conversion of methanol can be up to 98.4%, and the DMMx selectivity reaches 34.1%, is particularly suitable for requiring to have the production process of higher DMMx yield.

Claims (9)

1. the catalyst of an oxidation conversion methyl alcohol, described catalyst contains at least a molecular sieve and metal component molybdenum and iron with acid catalysis activity, with the catalyst is benchmark, the content of described molecular sieve is 40～95 weight %, in oxide, the content of described metal component molybdenum is 0.5～50 weight %, and the ferrous metal components contents is 0.2～20 weight %.
2. catalyst according to claim 1 is characterized in that, is benchmark with the catalyst, the content of described molecular sieve is 70～90 weight %, in oxide, the content of described metal component molybdenum is 2～20 weight %, and the content of metal component iron is 0.2～10 weight %.
3. method according to claim 1 and 2 is characterized in that, described molecular screening with acid catalysis activity is from the molecular sieve with central hole structure and have in the molecular sieve of macroporous structure one or more.
4. catalyst according to claim 3 is characterized in that, described molecular screening with central hole structure is from ZSM-5, and the molecular screening with macroporous structure is from Y zeolite.
5. catalyst according to claim 4 is characterized in that described Y zeolite is selected from one or more among HY, REY, REHY, USY, the REUSY.
6. catalyst according to claim 5 is characterized in that described Y zeolite is selected from one or more among REY, REHY, the REUSY.
7. catalyst according to claim 1 is characterized in that, contains heat-resistant inorganic oxide matrix in the described catalyst, is benchmark with the catalyst, and the content of described heat-resistant inorganic oxide matrix is less than 80 weight %.
8. catalyst according to claim 7, it is characterized in that, described heat-resistant inorganic oxide matrix is selected from one or more in aluminium oxide, silica, the silica-alumina, is benchmark with the catalyst, and the content of described heat-resistant inorganic oxide matrix is less than 60 weight %.
9. catalyst according to claim 8 is characterized in that described heat-resistant inorganic oxide matrix is selected from aluminium oxide, is benchmark with the catalyst, and the content of described heat-resistant inorganic oxide matrix is less than 25 weight %.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102030621A (en) * 2009-09-29 2011-04-27 中国石油化工股份有限公司 Process for generating DMMx from methanol by gas phase method
CN108212197A (en) * 2018-01-23 2018-06-29 西南化工研究设计院有限公司 A kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether and its preparation and application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1037667C (en) * 1991-03-20 1998-03-11 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
CN1166438C (en) * 2002-09-28 2004-09-15 太原理工大学 Nitrogen oxide purifying catalyst and preparation thereof
CN101451074B (en) * 2007-11-28 2012-03-21 中国石油化工股份有限公司 Catalyst for heavy oil catalytic cracking and preparation method thereof
CN101322945B (en) * 2008-08-01 2010-08-04 中国海洋石油总公司 Method for preparing sulphur-containing condensate oil modifying catalyst and use

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102030621A (en) * 2009-09-29 2011-04-27 中国石油化工股份有限公司 Process for generating DMMx from methanol by gas phase method
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
CN108212197A (en) * 2018-01-23 2018-06-29 西南化工研究设计院有限公司 A kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether and its preparation and application

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