CN104437598A - Polyoxymethylene dimethyl ether (PODE) regular structure catalyst - Google Patents
Polyoxymethylene dimethyl ether (PODE) regular structure catalyst Download PDFInfo
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Abstract
The invention relates to a polyoxymethylene dimethyl ether (PODE) regular structure catalyst, a preparation method and a PODE synthesis method, mainly aiming at solving the technical problem that the catalyst dosage is great under the condition that the activity of a catalyst is considerable in the prior art. The PODE regular structure catalyst is composed of a skeleton carrier and a molecular sieve coating, and an active coating is selected from at least one of a beta zeolite molecular sieve, a ZSM-5 molecular sieve, and an MCM-22 or MCM-56 zeolite molecular sieve. The technical problem is well solved, and the technology can be used for industrial production of the PODE catalyst.
Description
Technical field
The present invention relates to polyoxymethylene dimethyl ether ordered structure catalyst, preparation method and polyoxymethylene dimethyl ether synthetic method.
Background technology
Polyoxymethylene dimethyl ether, i.e. Polyoxymethylene dimethyl ethers (PODE), be the common name of a class material, its skeleton symbol can be expressed as CH
3o (CH
2o)
ncH
3, there is higher Cetane number (> 40) and oxygen content (42 ~ 51%).When the value of n is 1, polyoxymethylene dimethyl ether is dimethoxym ethane, although use dimethoxym ethane also can improve efficiency of energy utilization as vehicle fuel addO-on therapy, reduces exhaust emissions, but still easily causes vent plug.When n value is 2 ~ 6, its physical property, combustibility and diesel oil closely, preferably resolve the defect that conventional additive exists as derv fuel blend component.Therefore polyoxymethylene dimethyl ether can be used as novel clean diesel component, and the addition in diesel oil can reach more than 10% (v/v), can improve diesel oil combustion position within the engine, improves the thermal efficiency, reduces the particle in tail gas and CO
xand NO
xdischarge.The optimum chain length of the polyoxymethylene dimethyl ether mixed with diesel oil is n=3,4.During n=2, the flash-point of polyoxymethylene dimethyl ether is too low, and when n is excessive, polyoxymethylene dimethyl ether may precipitate blocking at low temperatures.It is reported, add the CH of 5 ~ 30%
3oCH
2oCH
3significantly can reduce NO
xdischarge.Add PODE and not only can replace part diesel oil, the efficiency of combustion of diesel oil can also be improved.Thus a kind of diesel fuel additives having application prospect is considered to.
As homologue, closely, they are highly stable in neutral and alkaline conditions for the chemical property of polyoxymethylene dimethyl ether and dimethoxym ethane, but can be hydrolyzed in acid condition and become methyl alcohol and formaldehyde.This series compound boiling spread, from 105 DEG C of n=2 to 242.5 DEG C of n=5, is difficult to by complete separated.
Polyoxymethylene dimethyl ether can use trace sulfuric acid or hydrochloric acid to be catalyst, prepared by the method for reacting by heating low polymerization degree paraformaldehyde or paraformaldehyde and methyl alcohol, when heating-up temperature is 150 DEG C, reaction time needs 15 hours, and reaction temperature rises to 165 ~ 180 DEG C of the reaction times can shorten to 12 hours.Portion of product can be caused with this understanding to resolve into hydrocarbon, also have part material generation side reaction to generate dimethyl ether in addition.The mean molecule quantity of polyoxymethylene dimethyl ether increases with the ratio of paraformaldehyde and methyl alcohol and increases, it is general when low polymerization degree paraformaldehyde or paraformaldehyde are 6: 1 with the ratio of methyl alcohol, the polymer of n=300 ~ 500 can be obtained, product sodium sulfite solution washs, and then passes through Crystallization Separation step by step.
EP1070755 describes and a kind ofly under three fluosulfonic acid exist, reacts by dimethoxym ethane and paraformaldehyde the method preparing in per molecule the polyoxymethylene dimethyl ether with 2 ~ 6 formaldehyde units.WO2006/045506A1 describes BASF AG and uses sulfuric acid, TFMS as catalyst, obtains the series product of n=1 ~ 10 with dimethoxym ethane, paraformaldehyde, metaformaldehyde for raw material.Above method all adopts Bronsted acid as catalyst, and this catalyst is cheap and easy to get, but corrosivity is strong, and be difficult to be separated, environmental pollution is large, the shortcoming high to the requirement of equipment.
CN 101182367A describes and adopts acidic ion liquid to be catalyst, is the method that reactant catalyzes and synthesizes polyoxymethylene dimethyl ether by methyl alcohol and metaformaldehyde.But ionic liquid also also exists equipment corrosion, and the separation and recovery of catalyst self and the problem of purification.
CN200910056819.9 and CN200910056820.1 describes and adopts solid acid to be catalyst, is the method that reactant catalyzes and synthesizes polyoxymethylene dimethyl ether by methyl alcohol and metaformaldehyde.But there is a large amount of side reaction product dimethoxym ethane in product, not high to the utilization rate of raw material.
The problems such as above-mentioned document all exists catalyst and has corrosivity, and product separating technique is complicated, and energy consumption is high, and in product, there is a large amount of accessory substance dimethoxym ethane, selectivity of product is poor, and raw material availability is not high.
It is the process that initial feed prepares polyoxymethylene dimethyl ether by methyl alcohol that EP2228359A1 describes a kind of.It is catalyst that the method uses through ammonium molybdate and Ferric nitrate modified molecular sieve, and methyl alcohol is obtained polyoxymethylene dimethyl ether with air (oxygen) oxidation step under temperature more than 200 DEG C conditions.The method production cost is relatively low, but catalyst preparation process is complicated, and polyoxymethylene dimethyl ether is selective unsatisfactory.But traditional molecular sieve catalyst, in order to the active catalyst consumption maintaining reaction is large.
Summary of the invention
One of technical problem to be solved by this invention is the technical problem that in prior art, catalyst amount is large when catalyst activity is suitable, a kind of new polyoxymethylene dimethyl ether ordered structure catalyst is provided, compared with traditional molecular sieve catalyst, have the advantages that to greatly reduce molecular sieve consumption when keeping catalyst activity and selectivity of product.
Two of technical problem to be solved by this invention is preparation methods of the polyoxymethylene dimethyl ether ordered structure catalyst corresponding to one of above-mentioned technical problem.
Three of technical problem to be solved by this invention is the polyoxymethylene dimethyl ether synthetic methods adopting one of above-mentioned technical problem described catalyst.
In order to one of solve the problems of the technologies described above, technical scheme of the present invention is as follows: polyoxymethylene dimethyl ether ordered structure catalyst, described ordered structure catalyst is made up of skeleton carrier and molecular sieve coating, and described active coating is selected from least one in beta-zeolite molecular sieve, ZSM-5 molecular sieve, MCM-22 or MCM-56 zeolite molecular sieve.
In ordered structure catalyst described in technique scheme, skeleton carrier preferably accounts for 60 ~ 99wt%, and described active coating preferably accounts for 1 ~ 40 wt%.Described active coating thickness is preferably 5 ~ 100 microns; Be more preferably 5 ~ 15 microns.
Those skilled in the art will know that, so-called ordered structure catalyst usually by skeleton matrix, dispersible carrier, active component and co-catalyst four part form, wherein active component, co-catalyst and dispersible carrier generally with the form load of coating on the inner surface of skeleton matrix cell walls.Ordered structure carrier serves as skeleton matrix, and it is generally made up of the carrier block of a whole block material, and inside is formed with the hollow pore passage structure in the macro-scale that is parallel to each other in a large number.
From those skilled in the art's angle, the shape of the present invention to skeleton carrier is not particularly limited, can cylinder, cuboid etc.; Also being not particularly limited duct shape, can be rectangle, circular, triangle etc.; From those skilled in the art, the material of skeleton carrier is not particularly limited, such as cordierite, pottery, metal etc.; The channel density of skeleton carrier is not particularly limited, but preferred 50 ~ 2000 cpsi.
In order to solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the preparation method of polyoxymethylene dimethyl ether ordered structure catalyst described in the described technical scheme of one of above-mentioned technical problem, comprises the steps:
(1) desired molecule sieve is distributed in water and makes the molecular sieve pulp that sieve particle d 90 is 1 ~ 30 micron; Molecular sieve pulp Middle molecule sieve particle is preferably 1 ~ 20 micron, more preferably 1 ~ 10 micron;
(2) described skeleton carrier is applied with the slurries that step (1) obtains;
(3) dry, roasting obtains described catalyst; Dry condition is preferred: 120 ~ 150 DEG C and 2 ~ 5 hours, roasting condition is preferred: 450 ~ 650 DEG C and 1 ~ 5 hour.
In order to increase molecular sieve coating thickness, the inventive method can repeat multiple operation (1) ~ (3) until reach required molecular sieve coating thickness.
In technique scheme, the preparation method of the molecular sieve pulp of step (1) is not particularly limited, and the mode preparing molecular sieve pulp conventional in prior art is all applicable to the present invention, but preferably adopts the mode of wet-milling.In order to obtain the molecular sieve pulp being more suitable for preparing catalyst of the present invention of stably dispersing, containing dispersant in preferred molecular sieve slurries.Dispersant finally can add making molecular sieve pulp, also can add in the process preparing molecular sieve pulp.Adopt wet-milling mode prepared slarry, preferably in the process of wet-milling, add dispersant.
In technique scheme, be not particularly limited the consumption of dispersant, within the scope of the understanding of those skilled in the art, but the weight ratio of preferred dispersants and molecular sieve is (0.01 ~ 20): 100.
In technique scheme, the dispersant preparing molecular sieve pulp conventional all can be used for the present invention; But in molecule, preferably there are polyhydroxy, one or more of completing in the compound of acidic group or polyoxyethylene groups poly-; One or more most preferably in polyethylene glycol, glycerine, polyvinyl alcohol or polyacrylic acid.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: polyoxymethylene dimethyl ether synthetic method, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 0.1 ~ 2.5: 0.01 ~ 12.5: 1, it is 50 ~ 200 DEG C in reaction temperature, reaction pressure is under the condition of 0.1 ~ 10MPa, and according to any one of the technical scheme of raw material and one of technical problem, ordered structure catalyst contacts, and reaction generates polyoxymethylene dimethyl ether.
Methyl alcohol in technique scheme: dimethoxym ethane: paraformaldehyde mol ratio is preferably 0.2 ~ 1: 0.1 ~ 4: 1.Raw material volume air speed is preferably 1000 ~ 10000hr
-1.Reaction temperature is preferably 80 ~ 150 DEG C.Reaction pressure is preferably 1 ~ 6MPa.
Adopt after the present invention, under condition on year-on-year basis, be only 10% of traditional catalyst at the selective molecular sieve consumption of n=3, achieve useful technique effect, can be used in the industrial production of polyoxymethylene dimethyl ether catalyst.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of catalyst:
By 24.81 grams (in butt, lower same) ZSM-5 type molecular sieve powder (d90=15 micron, Si/Al=150 Catalyst Factory, Nankai Univ product) mix with 74. 44 grams of deionized waters, wet ball grinding becomes molecular sieve pulp, sieve particle diameter d 90=6 microns, the polyethylene glycol PEG400 aqueous solution 0.75 gram (in solution, the percetage by weight of polyethylene glycol is 2 wt%) is added in slurries, the addition of this solution is 3 wt% of molecular sieve, stir and obtain coating slurry in 25 minutes, coating slurry Middle molecule sieve content is 24.81 wt%.
By 1 liter of honeycomb substrate (cordierite honeycomb carrier, diameter 5CM, long 5CM, duct number 400 cpsi per square inch on cross section) mix with 2 liters of coating slurry, with the coating slurry that flow velocity is the removing flowing in 15 minutes of 10 meter per second normal temperature (25 DEG C) air purging carrier duct, dry 4 hours at 120 DEG C, roasting 2 hours at 650 DEG C, obtains the honeycomb structured catalyst configurations with molecular sieve catalyst coating.Wherein, in catalyst, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 2]
The preparation of catalyst:
Removing coating active component be MCM-56 (Si/Al=100) outward, his process is identical with embodiment 1.Wherein, in catalyst, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 3]
The preparation of catalyst:
Removing coating active component be β zeolite (Si/Al=150) outward, other processes are identical with embodiment 1.Wherein, in catalyst, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 4]
The preparation of catalyst:
Removing coating active component be MCM-22 (Si/Al=150) outward, other processes are identical with embodiment 1.Wherein, in catalyst, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 5]
The preparation of catalyst:
Identical with embodiment 1.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 200 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 6]
The preparation of catalyst:
Removing coating active component be MCM-56 (Si/Al=100) outward, other processes are identical with embodiment 1.Wherein, in catalyst, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 180 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 7]
The preparation of catalyst:
Identical with embodiment 1.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 5MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 8]
The preparation of catalyst:
Identical with embodiment 1.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 4: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 9]
The preparation of catalyst:
Identical with embodiment 1.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 1000hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 10]
The preparation of catalyst:
Removing coating active component be ZSM-5 (Si/Al=100) outward, other processes are identical with embodiment 1.Wherein, in catalyst, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[embodiment 11]
The preparation of catalyst:
By 12.40 grams (in butt, lower same) ZSM-5 type molecular sieve powder (d90=15 micron, Si/Al=150 Catalyst Factory, Nankai Univ product), 12.40 grams of MCM-56 (Si/Al=100) mix with 74. 44 grams of deionized waters, wet ball grinding becomes molecular sieve pulp, sieve particle diameter d 90=6 microns, the polyethylene glycol PEG400 aqueous solution 0.75 gram (in solution, the percetage by weight of polyethylene glycol is 2 wt%) is added in slurries, the addition of this solution is 3 wt% of molecular sieve, stir and obtain coating slurry in 25 minutes, coating slurry Middle molecule sieve content is 24.75 wt%.
By 1 liter of honeycomb substrate (cordierite honeycomb carrier, diameter 5CM, long 5CM, duct number 400 cpsi per square inch on cross section) mix with 2 liters of coating slurry, with the coating slurry that flow velocity is the removing flowing in 15 minutes of 10 meter per second normal temperature (25 DEG C) air purging carrier duct, dry 4 hours at 120 DEG C, roasting 2 hours at 650 DEG C, obtains the honeycomb structured catalyst configurations with molecular sieve catalyst coating.Wherein, in catalyst, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[comparative example 1]
The preparation of molecular sieve catalyst: adopt ZSM-5 molecular sieve (Si/Al=150) 150g, mix with above-mentioned molecular sieve with 30g adhesive boehmite, add 3g sesbania powder extrusion aid, shaping on F-26 type double screw banded extruder, 450 DEG C of roastings 2 hours, obtained diameter is 5CM, length is 5CM, the column type molecular sieve of duct number 400 cpsi per square inch on cross section.Wherein molecular sieve content 80 wt%.
Evaluating catalyst:
Fix at 500 milliliters of fixed bed reactors and above-mentionedly prepare gained 100 milliliters of catalyst, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, raw material volume air speed 2500hr
-1, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1 is 150 DEG C in reaction temperature, reaction pressure is under the condition of 2MPa, reacts after 4 hours and samples, through gas chromatographic analysis, comprise polyoxymethylene dimethyl ether and unreacted raw material in sample, its composition distribution is as table 1.
[0053] table 1
Claims (9)
1. polyoxymethylene dimethyl ether ordered structure catalyst, described ordered structure catalyst is made up of skeleton carrier and molecular sieve coating, and described active coating is selected from least one in beta-zeolite molecular sieve, ZSM-5 molecular sieve, MCM-22 or MCM-56 zeolite molecular sieve.
2. ordered structure catalyst according to claim 1, it is characterized in that in described ordered structure catalyst, skeleton carrier accounts for 60 ~ 99wt%, described active coating accounts for 1 ~ 40 wt%.
3. ordered structure catalyst according to claim 1, is characterized in that described active coating thickness is 5 ~ 100 microns.
4. the preparation method of the ordered structure catalyst of polyoxymethylene dimethyl ether described in claim 1, comprises the steps:
(1) desired molecule sieve is distributed in water and makes the molecular sieve pulp that sieve particle d 90 is 1 ~ 30 micron;
(2) described skeleton carrier is applied with the slurries that step (1) obtains;
(3) dry, roasting obtains described catalyst.
5. preparation method according to claim 4, is characterized in that the molecular sieve pulp of step (1) adopts the mode of wet-milling to prepare.
6. preparation method according to claim 5, is characterized in that adding dispersant in the wet-milling process of step (1).
7. preparation method according to claim 5, is characterized in that adding dispersant in the molecular sieve pulp that step (1) obtains.
8. the preparation method according to claim 6 or 7, is characterized in that described dispersant is selected from molecule and has polyhydroxy, one or more of completing in the compound of acidic group or polyoxyethylene groups poly-.
9. polyoxymethylene dimethyl ether synthetic method, with methyl alcohol, dimethoxym ethane and paraformaldehyde for raw material, wherein methyl alcohol: dimethoxym ethane: paraformaldehyde mol ratio is 0.1 ~ 2.5: 0.01 ~ 12.5: 1, it is 50 ~ 200 DEG C in reaction temperature, reaction pressure is under the condition of 0.1 ~ 10MPa, raw material contacts with ordered structure catalyst according to any one of claims 1 to 3, and reaction generates polyoxymethylene dimethyl ether.
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| CN101768058A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether |
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| CN103285905B (en) * | 2012-02-29 | 2015-03-04 | 北京安耐吉能源工程技术有限公司 | Overall structure catalyst, preparation method of overall structure catalyst, and method for preparing caprolactam |
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| CN101768058A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether |
| CN102040491A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves |
| CN102000559A (en) * | 2010-11-18 | 2011-04-06 | 中国海洋石油总公司 | Method for preparing dimethoxymethane by adopting supported niobium oxide catalyst |
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