CN101817731A - Method for preparing polymethoxy dimethyl ether by converting methanol - Google Patents
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Abstract
The invention provides a method for preparing polymethoxy dimethyl ether by converting methanol, which comprises the step of: performing the contact reaction on the methanol and an oxidizer in the presence of a catalyst, wherein the catalyst contains at least one metal component selected from a VIB group, at least one metal component selected from a VIII group and at least one molecular sieve with acid catalytic activity; based on the catalyst, the content of the molecular sieve is 40 to 95 weight percent; and based on oxides, the content of the metal component of the VIB group is 0.5 to 50 weight percent and the content of the metal component of the VIII group is 0.2 to 20 weight percent.
Description
Technical field
The present invention relates to a kind of oxidation methanol conversion method, more specifically to a kind of be the method for DMMx (polymethoxy dimethyl ether) by oxidation conversion methyl alcohol.
Background technology
With methyl alcohol is all kinds of useful chemical of raw material production, is the importance of C1 technical study always.
For example, in the presence of catalyzer, the methanol dehydration dimethyl ether synthesis.Dme has good combustioncharacteristics, and the cetane value height can be widely used in civil LPG substitute and onboard fuel.In addition, dme can also be as uses such as the propelling agent of aerosol, whipping agent, solvent, extraction agents.
US6166266 discloses a kind of with formaldehyde with contain the raw material of dme, and the ion exchange resin of making catalyzer or having a protonic acid with the borosilicate with MFI structure is catalyzer, synthetic polymethoxy dimethyl ether (CH
3O (CH
2O)
xCH
3, be abbreviated as DMM
X, 2≤x≤8) method.
It is raw material with methylal and polyoxymethylene that EP1505049A1 discloses a kind of, utilizes halogenosulfonic acid to be catalyzer, the method for synthetic polymethoxy dimethyl ether (DMMx, 2≤x≤5).
Polymethoxy dimethyl ether (DMM
X) have higher cetane value (＞60) equally, can be used as compression-ignited diesel motor fuel or diesel-dope 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 method of new oxidation conversion methyl alcohol.
The invention provides a kind of method of preparing polymethoxy dimethyl ether by converting methanol, being included in catalyzer exists down methyl alcohol and oxygenant contact reacts, it is characterized in that, described catalyzer contains at least a metal component that is selected from group vib, at least a metal component that is selected from group VIII and at least aly have an active molecular sieve of acid catalysis, with the catalyzer is benchmark, the content of described molecular sieve is 40 weight %～95 weight %, in oxide compound, the content of the metal component of described group vib is 0.5 weight %～50 weight %, and the metal component content of group VIII is 0.2 weight %～20 weight %.
Compared with prior art, method provided by the invention can directly be dme and polymethoxy dimethyl ether (DMM with methanol conversion through single step reaction
X, 2≤x≤8).
Embodiment
According to method provided by the invention, wherein, the metal component of the group vib in the described catalyzer is preferably molybdenum, and the metal component of group VIII is preferably iron, described metal component can be to exist with different shapes such as its corresponding salt, oxide compound or sulfide, and preferably the oxide compound with them exists.In oxide compound and with the catalyzer is benchmark, and the content of the metal component of described group vib is preferably 2 weight %～20 weight %, and the metal component content of group VIII is preferably 0.2 weight %～10 weight %.
Described have the active molecular sieve of acid catalysis preferably from having in the molecular sieve of central hole structure and/or macroporous structure one or more, and preferred mesoporous molecular sieve is ZSM-5, further preferred SiO
2/ Al
2O
3(mol ratio) is 〉=50 ZSM-5, and the 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 catalyzer is benchmark, and the content of described molecular sieve is preferably 60 weight %～90 weight %, more 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, have an active molecular sieve of acid catalysis with this solution impregnation is described again, the method preparation of dry afterwards, roasting or not roasting.The method of described drying and roasting and condition are preparation catalyzer customary way and condition.Preferred drying conditions 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 time of drying, 400～600 ℃ of further preferred temperature, 1～4 hour time.
According to method provided by the invention, wherein said catalyzer can be the forming composition of various easy handlings, 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 catalyzer was the forming composition of various easy handlings, described moulding can be at first with described molecular sieve molded, afterwards the loaded 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 moulding 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 gum, starch, polyvinyl alcohol, the poly-ethanol.
According to method provided by the invention, wherein, preferably also contain heat-resistant inorganic oxide matrix in the described catalyzer, be benchmark with the catalyzer, the content of described heat-resistant inorganic oxide matrix is no more than 80 weight %, preferably is no more than 60 weight %.
Described heat-resistant inorganic oxide matrix is the heat-resistant inorganic oxide of Chang Zuowei catalyst support substrate.For example, be selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, the silica-alumina-zirconium white one or more.In the preferred aluminum oxide, silicon oxide, silica-alumina wherein one or more.
When also containing heat-resistant inorganic oxide matrix in the described catalyzer, 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 conditions 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 time of drying, 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 catalyzer, 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 conditions comprises: 50～300 ℃ of temperature, 0.5～12 hour time, 100～200 ℃ of further preferred temperature, 1～6 hour time; Preferred roasting condition comprises: 350～600 ℃ of temperature, 0.5～8 hour time of drying, 400～500 ℃ of further preferred temperature, 1～4 hour time.
According to method provided by the invention, wherein, described oxygenant preferably is the gaseous mixture of inert reaction from oxygen or oxygen and other with methyl alcohol under described reaction conditions.The gas that described and methyl alcohol are inert reaction is one or more in air, nitrogen or rare gas element preferably.The content of oxygen is 1～30% in the described gas mixture.
Being enough to make described methyl alcohol and oxygenant under catalytic prerequisite under the described reaction conditions, reaction unit is not particularly limited according to method provided by the present invention.For example, described reaction unit can be intermittent type tank reactor, fixed-bed reactor, fluidized-bed reactor etc.Described catalytic condition comprises: temperature of reaction is 50～500 ℃, and reaction pressure is 0.1MPa～10MPa, and the mass space velocity of methanol feeding is 0.5～50h
-1, the consumption of described oxygenant makes that the molar ratio of oxygen and methyl alcohol is 0.01～0.5 in the described contact reacts.Described catalytic preferred condition comprises: temperature of reaction is 100～400 ℃, more preferably 100～300 ℃, more be preferably 200～300 ℃, reaction pressure is 0.1MPa～5MPa, 0.1MPa～2MPa more preferably, the mass space velocity of methanol feeding is 3～30h
-1, 8～20h more preferably
-1, the consumption of described oxygenant makes that the molar ratio of oxygen and methyl alcohol is 0.05～0.3 in the described contact reacts.
According to method provided by the invention, this product mixture comprises dme, polymethoxy dimethyl ether and water.The operating unit that optionally can comprise one or more flash distillations, air distillation and underpressure distillation usually is to realize desirable separation.
Further specify the present invention below by example, but the present invention is not limited to this.
Embodiment 1～11 explanation is suitable for the Catalysts and its preparation method of the inventive method.
Example 1
51g ammonium molybdate and 5g iron 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 catalyzer C1 in 1 hour.The composition of catalyzer C1 is listed in the table 1.
Example 2
51g ammonium molybdate and 5g iron 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 catalyzer C2 in 1 hour.The composition of catalyzer C2 is listed in the table 1.
Example 3
51g ammonium molybdate and 5g iron 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 catalyzer C3 in 1 hour.The composition of catalyzer C3 is listed in the table 1.
Example 4
80g ammonium molybdate and 4g iron 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 catalyzer C4 in 1 hour.The composition of catalyzer C4 is listed in the table 1.
Example 5
51g ammonium molybdate and 5g iron 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 catalyzer is placed 200 ℃ of baking ovens dry 2 hours, and obtained catalyzer C5.The composition of catalyzer C5 is listed in the table 1.
Example 6
51g ammonium molybdate and 5g iron 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 catalyzer C6 in 1 hour.The composition of catalyzer C6 is listed in the table 1.
Example 7
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 cylinder shape 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 catalyzer C7 in 1 hour.The composition of catalyzer C7 is listed in the table 1.
Example 8
With the SiO of 700g REY molecular sieve (rare earth mass content 6%, Chang Ling catalyst plant product) with weight percent meter 30%
2-Al
2O
3Mix, 51g ammonium molybdate and 5g iron 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 catalyzer C8 in 1 hour.The composition of catalyzer C8 is listed in the table 1
Example 9
102g ammonium molybdate and 10g iron 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 catalyzer is placed 200 ℃ of baking ovens dry 2 hours, and obtained catalyzer C9.The composition of catalyzer C9 is listed in the table 1.
Table 1
| Embodiment | Catalyzer | Molecular sieve, % | Matrix, % | Molybdenum oxide, % | Ferric oxide, % |
| ??1 | ??C1 | ??86.48 | ??0 | ??8.40 | ??5.12 |
| ??2 | ??C2 | ??90.18 | ??0 | ??8.36 | ??1.46 |
| ??3 | ??C3 | ??90.71 | ??0 | ??8.67 | ??0.62 |
| ??4 | ??C4 | ??87.57 | ??0 | ??11.96 | ??0.47 |
| ??5 | ??C5 | ??91.83 | ??0 | ??7.61 | ??0.56 |
| ??6 | ??C6 | ??95.08 | ??0 | ??4.57 | ??0.35 |
| Embodiment | Catalyzer | Molecular sieve, % | Matrix, % | Molybdenum oxide, % | Ferric oxide, % |
| ??7 | ??C7 | ??83.60 | ??8.36 | ??7.62 | ??0.42 |
| ??8 | ??C8 | ??71.16 | ??21.35 | ??7.12 | ??0.37 |
| ??9 | ??C9 | ??75.42 | ??0 | ??17.06 | ??7.52 |
Example 10～23 explanations the invention provides method and effect thereof.
Be reflected in the fixed-bed reactor and carry out, material benzenemethanol is the analytical pure product of Beijing Chemical Plant, and containing oxygenant is air.Wherein, catalyzer C1～C6, C9 through compressing tablet, fragmentation, be screened into 20～40 purpose particles, bar shaped catalyst C7～C8 through broken, be screened into 20～40 purpose particles.
Each embodiment lists in table 2 with catalyzer and reaction conditions.
React sampling 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 4 molecular sieves respectively through compressing tablet, fragmentation, be screened into 20～40 purpose particles, and adopt example 10 reaction conditionss to estimate, the results are shown in table 3.
Table 2
| Embodiment | Catalyzer | Temperature, ℃ | Pressure, MPa | Air speed, h -1 | Oxygen/methyl alcohol |
| ??10 | ??C1 | ??250 | ?0.3 | ?13 | ??0.30 |
| ??11 | ??C2 | ??150 | ?0.3 | ?10 | ??0.15 |
| ??12 | ??C2 | ??250 | ?0.4 | ?13 | ??0.20 |
| ??13 | ??C3 | ??250 | ?1.1 | ?13 | ??0.20 |
| ??14 | ??C3 | ??250 | ?0.3 | ?13 | ??0.25 |
| ??15 | ??C4 | ??250 | ?0.5 | ?13 | ??0.20 |
| ??16 | ??C5 | ??250 | ?0.4 | ?13 | ??0.20 |
| ??17 | ??C5 | ??250 | ?1.6 | ?13 | ??0.30 |
| Embodiment | Catalyzer | Temperature, ℃ | Pressure, MPa | Air speed, h -1 | Oxygen/methyl alcohol |
| ??18 | ??C6 | ??350 | ?0.3 | ?20 | ??0.10 |
| ??19 | ??C6 | ??250 | ?0.2 | ?13 | ??0.20 |
| ??20 | ??C7 | ??250 | ?1.6 | ?13 | ??0.10 |
| ??21 | ??C8 | ??300 | ?1.1 | ?13 | ??0.10 |
| ??22 | ??C9 | ??250 | ?1.1 | ?13 | ??0.20 |
| ??23 | ??C9 | ??250 | ?0.3 | ?13 | ??0.20 |
Table 3
| Embodiment | Catalyzer | Methanol conversion/% | DMMx selectivity/% |
| ??10 | ??C1 | ??83.4 | ??7.1 |
| ??11 | ??C2 | ??81.4 | ??15.9 |
| ??12 | ??C2 | ??82.9 | ??16.2 |
| ??13 | ??C3 | ??97.2 | ??26.4 |
| ??14 | ??C3 | ??96.0 | ??26.1 |
| ??15 | ??C4 | ??97.6 | ??31.7 |
| ??16 | ??C5 | ??97.1 | ??26.6 |
| ??17 | ??C5 | ??98.4 | ??34.1 |
| ??18 | ??C6 | ??87.1 | ??10.9 |
| ??19 | ??C6 | ??84.9 | ??11.7 |
| ??20 | ??C7 | ??94.1 | ??21.4 |
| ??21 | ??C8 | ??89.2 | ??17.2 |
| ??22 | ??C9 | ??97.4 | ??27.9 |
| Embodiment | Catalyzer | Methanol conversion/% | DMMx selectivity/% |
| ??23 | ??C9 | ??93.5 | ??24.2 |
| 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 dme and polymethoxy dimethyl ether (DMM with methanol conversion through single step reaction
X, 2≤x≤8), particularly as embodiment 17, when the molecular sieve that is adopted in the described catalyzer 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 (14)
1. the method for a preparing polymethoxy dimethyl ether by converting methanol, being included in catalyzer exists down methyl alcohol and oxygenant contact reacts, it is characterized in that, described catalyzer contains at least a metal component that is selected from group vib, at least a metal component that is selected from group VIII and at least aly have an active molecular sieve of acid catalysis, with the catalyzer is benchmark, the content of described molecular sieve is 40 weight %～95 weight %, in oxide compound, the content of the metal component of described group vib is 0.5 weight %～50 weight %, and the metal component content of group VIII is 0.2 weight %～20 weight %.
2. method according to claim 1, it is characterized in that, the metal component of the group vib in the described catalyzer is a molybdenum, the metal component of group VIII is an iron, in oxide compound and with the catalyzer is benchmark, the content of the metal component of described group vib is 2 weight %～20 weight %, and the metal component content of group VIII is 0.2 weight %～10 weight %.
3. method according to claim 1, it is characterized in that, described have the active molecular screening of acid catalysis from the molecular sieve with central hole structure with have in the molecular sieve of macroporous structure one or more, is benchmark with the catalyzer, and the content of described molecular sieve is 70 weight %～90 weight %.
4. method 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. method 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. method according to claim 5 is characterized in that described Y zeolite is selected from one or more among REY, REHY, the REUSY.
7. method according to claim 1 is characterized in that, contains heat-resistant inorganic oxide matrix in the described catalyzer, is benchmark with the catalyzer, and the content of described heat-resistant inorganic oxide matrix is no more than 80 weight %.
8. method according to claim 7, it is characterized in that, described heat-resistant inorganic oxide matrix is selected from one or more in aluminum oxide, silicon oxide, the silica-alumina, is benchmark with the catalyzer, and the content of described heat-resistant inorganic oxide matrix is no more than 60 weight %.
9. method according to claim 1 is characterized in that, described catalytic condition comprises: temperature of reaction is 50～500 ℃, and reaction pressure is 0.1MPa～10MPa, and the mass space velocity of methanol feeding is 0.5～50h
-1, the consumption of described oxygenant makes that the molar ratio of oxygen and methyl alcohol is 0.01～0.5 in the described contact reacts
10. method according to claim 9 is characterized in that, described catalytic condition comprises: temperature of reaction is 100～400 ℃, and reaction pressure is 0.1MPa～5MPa, and the mass space velocity of methanol feeding is 3～30h
-1, the consumption of described oxygenant makes that the molar ratio of oxygen and methyl alcohol is 0.05～0.3 in the described contact reacts.
11. method according to claim 10 is characterized in that, described catalytic condition comprises: temperature of reaction is 200～300 ℃, and reaction pressure is 0.1MPa～2MPa, and the mass space velocity of methanol feeding is 8～20h
-1
12. method according to claim 1 is characterized in that, described oxygenant is selected from air, air or oxygen and other are the mixture of the gas of inert reaction with methyl alcohol under described reaction conditions.
13. method according to claim 12 is characterized in that, the gas that described and methyl alcohol are inert reaction is selected from one or more in nitrogen or the rare gas element.
14. method according to claim 11 is characterized in that, the content of oxygen is 1～30% in the described gas mixture.
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| 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 |
| CN103508860A (en) * | 2012-06-15 | 2014-01-15 | 华东理工大学 | Method for preparing polyoxymethylene dimethylethers from methanol and formaldehyde |
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| US6350919B1 (en) * | 1998-11-12 | 2002-02-26 | Bp Corporation North America Inc. | Preparation of polyoxymethylene dialkane ethers, by catalytic conversion of formaldehyde formed by dehydrogenation of methanol or dimethyl ether |
| US6160186A (en) * | 1998-11-12 | 2000-12-12 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by dehydrogenation of dimethyl ether |
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| 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 |
| CN103508860A (en) * | 2012-06-15 | 2014-01-15 | 华东理工大学 | Method for preparing polyoxymethylene dimethylethers from methanol and formaldehyde |
| CN103508859A (en) * | 2012-06-15 | 2014-01-15 | 华东理工大学 | Method for preparing polyoxymethylene dimethyl ethers |
| CN103508859B (en) * | 2012-06-15 | 2015-07-15 | 华东理工大学 | Method for preparing polyoxymethylene dimethyl ethers |
| CN103508860B (en) * | 2012-06-15 | 2015-07-15 | 华东理工大学 | Method for preparing polyoxymethylene dimethylethers from methanol and formaldehyde |
| CN103880612A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Method for synthesizing polyoxymethylene dimethyl ether from paraformaldehyde |
| CN103880612B (en) * | 2012-12-19 | 2015-10-21 | 中国石油化工股份有限公司 | By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers |
| CN104230684A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Process for synthesis of polyoxymethylene dimethyl ether from methyl |
| CN104230684B (en) * | 2013-06-17 | 2016-09-07 | 中国石油化工股份有限公司 | Process by methanol-fueled CLC polyoxymethylene dimethyl ether |
| CN104276932A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of paraform dimethyl ether |
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