CN104437598B - Polyoxymethylene dimethyl ether ordered structure catalyst - Google Patents
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Abstract
The present invention relates to polyoxymethylene dimethyl ether ordered structure catalyst, preparation method and polyoxymethylene dimethyl ether synthetic method, mainly solve the big technical problem of catalyst amount in the case where catalyst activity is suitable in the prior art, the present invention is by using polyoxymethylene dimethyl ether ordered structure catalyst, described ordered structure catalyst is made up of skeleton carrier and molecular sieve coating, the active coating is selected from beta-zeolite molecular sieve, the molecular sieves of ZSM 5, at least one technical scheme in MCM 22 or the zeolite molecular sieves of MCM 56, preferably solve the technical problem, in industrial production available for polyoxymethylene dimethyl ether 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), are the logical of a class material
Claim, its skeleton symbol can be expressed as CH3O(CH2O)nCH3, with higher Cetane number (>40) with oxygen content (42~51%).Work as n
Value be 1 when, polyoxymethylene dimethyl ether is dimethoxym ethane, although can also be improved using dimethoxym ethane as vehicle fuel addO-on therapy
Efficiency of energy utilization, reduces exhaust emissions, but still easily cause vent plug.When n values are 2~6, its physical property, combustibility
With diesel oil closely, the defect that conventional additive exists as derv fuel blend component is preferably resolved.Therefore poly- first
Aldehyde dimethyl ether can be as new cleaning diesel component, and the addition in diesel oil can improve bavin up to more than 10% (v/v)
The combustion position of oil within the engine, improves the particulate matter and CO in the thermal efficiency, reduction tail gasxAnd NOxDischarge.With diesel oil
The a length of n=3,4 of the optimal chain of polyoxymethylene dimethyl ether of mixing.During n=2, the flash-point of polyoxymethylene dimethyl ether is too low, and n it is excessive when, poly- first
Aldehyde dimethyl ether may precipitate blocking at low temperature.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be greatly reducedxDischarge.
Addition PODE can not only replace part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil.It is considered as thus a kind of great application
The diesel fuel additives of prospect.
As homologue, closely, they are in neutral and alkaline bar for the chemical property and dimethoxym ethane of polyoxymethylene dimethyl ether
It is highly stable under part, but can hydrolyze in acid condition as methanol and formaldehyde.This series compound boiling spread is from n=2's
105 DEG C to 242.5 DEG C of n=5, it is difficult to be completely distilled off separation.
It is catalyst that polyoxymethylene dimethyl ether, which can use trace sulfuric acid or hydrochloric acid, by heat low polymerization degree paraformaldehyde or
Prepared by the method that paraformaldehyde reacts with methanol, when heating-up temperature is 150 DEG C, and the reaction time needs 15 hours, reaction temperature
Rising to 165~180 DEG C of the reaction times can shorten to 12 hours.Portion of product can be caused to resolve into carbon oxygen on this condition
Compound, also has part material to occur side reaction generation dimethyl ether in addition.The mean molecule quantity of polyoxymethylene dimethyl ether is with poly first
The ratio of aldehyde and methanol increases and increased, general when the ratio between low polymerization degree paraformaldehyde or paraformaldehyde and methanol are 6: 1, can
To obtain the polymer of n=300~500, product is washed with sodium sulfite solution, then passes through Crystallization Separation step by step.
EP1070755 describes one kind and prepares per molecule by dimethoxym ethane and paraformaldehyde reaction in the presence of three fluosulfonic acid
In have 2~6 formaldehyde units polyoxymethylene dimethyl ether method.WO2006/045506A1 describes BASF AG and uses sulphur
Acid, trifluoromethanesulfonic acid have obtained the series production of n=1~10 using dimethoxym ethane, paraformaldehyde, metaformaldehyde as catalyst as raw material
Thing.Above method is using Bronsted acid as catalyst, and this catalyst is cheap and easy to get, but corrosivity is strong, it is difficult to separate, environment
Pollution is big, the high shortcoming of the requirement to equipment.
CN101182367A, which is described, uses acidic ion liquid for catalyst, is reactant by methanol and metaformaldehyde
The method for catalyzing and synthesizing polyoxymethylene dimethyl ether.But ionic liquid is returned there is also equipment corrosion, and the separation of catalyst itself
The problem of receiving and purify.
CN200910056819.9 and CN200910056820.1, which are described, uses solid acid for catalyst, by methanol and
The method that metaformaldehyde catalyzes and synthesizes polyoxymethylene dimethyl ether for reactant.But there are a large amount of side reaction product first contractings in product
Aldehyde, the utilization rate to raw material is not high.
There is the problems such as catalyst has corrosivity, product separating technique complexity, high energy consumption, and reaction production in above-mentioned document
There are a large amount of accessory substance dimethoxym ethanes in thing, selectivity of product is poor, and raw material availability is not high.
EP2228359A1 describes a kind of process for preparing polyoxymethylene dimethyl ether for initial feed by methanol.The party
It is catalyst that method, which is used by ammonium molybdate and Ferric nitrate modified molecular sieve, by methanol under 200 DEG C of conditions above of temperature with sky
The oxidation of the step of gas (oxygen) one obtains polyoxymethylene dimethyl ether.This method production cost is relatively low, but catalyst preparation process is complicated,
And the selectivity of polyoxymethylene dimethyl ether is unsatisfactory.But traditional molecular sieve catalyst, for the active catalyst of maintenance reaction
Consumption is big.
The content of the invention
One of technical problems to be solved by the invention are to be catalyzed in the prior art in the case where catalyst activity is suitable
The big technical problem of agent consumption is there is provided a kind of new polyoxymethylene dimethyl ether ordered structure catalyst, with traditional molecular sieve catalytic
Agent is compared, with the characteristics of can greatly reduce molecular sieve consumption in the case of keeping catalyst activity and selectivity of product.
The two of the technical problems to be solved by the invention are polyoxymethylene dimethyl ether rule corresponding with one of above-mentioned technical problem
The preparation method of whole structure catalyst.
The three of the technical problems to be solved by the invention are the polyformaldehyde using one of the above-mentioned technical problem catalyst
DME synthesis method.
One of in order to solve the above-mentioned technical problem, technical scheme is as follows：Polyoxymethylene dimethyl ether ordered structure is urged
Agent, described ordered structure catalyst is made up of skeleton carrier and molecular sieve coating, and the active coating is selected from β zeolite molecules
At least one in sieve, ZSM-5 molecular sieve, MCM-22 or MCM-56 zeolite molecular sieves.
Ordered structure catalyst middle skeleton carrier described in above-mentioned technical proposal preferably accounts for 60~99wt%, the activity
Coating preferably accounts for 1~40wt%.The active coating thickness is preferably 5~100 microns；More preferably 5~15 microns.
One skilled in the art will appreciate that so-called ordered structure catalyst is generally by skeleton matrix, dispersible carrier, active component
And the part of co-catalyst four composition, wherein active component, co-catalyst and dispersible carrier are typically supported in the form of coating
On the inner surface of skeleton matrix cell walls.Ordered structure carrier serves as skeleton matrix, and it is typically by the carrier block of a whole block material
Constitute, inside is formed with the hollow pore passage structure in the macro-scale being largely parallel to each other.
From those skilled in the art's angle, the shape of skeleton carrier is not particularly limited the present invention, can be with cylinder
Body, cuboid etc.；Device to hole road shape is circular it is not also specifically limited, can be rectangle, triangle etc.；From art technology
Personnel set out, and the material to skeleton carrier is not particularly limited, for example cordierite, ceramics, metal etc.；To the passage of skeleton carrier
Density is not particularly limited, but preferably 50~2000cpsi.
In order to solve the above-mentioned technical problem two, technical scheme is as follows：One of above-mentioned technical problem skill
The preparation method of polyoxymethylene dimethyl ether ordered structure catalyst, comprises the following steps described in art scheme：
(1) required molecular sieve is distributed to the molecular sieve pulp for being made that sieve particle d90 is 1~30 micron in water;Point
Sieve particle is preferably 1~20 micron in sub- screening the pulp liquid, more preferably 1~10 micron；
(2) slurries obtained with step (1) coat the skeleton carrier；
(3) dry, roasting obtains the catalyst；Dry condition is preferred：120~150 DEG C and 2~5 hours, it is calcined bar
Part is preferred:450~650 DEG C and 1~5 hour.
In order to increase molecular sieve coating thickness, the inventive method can repeat operate (1)~(3) needed for reaching again
Molecular sieve coating thickness.
Step in above-mentioned technical proposal（1）The preparation method of molecular sieve pulp be not particularly limited, in the prior art often
The mode for preparing molecular sieve pulp is applied to the present invention, and it is preferable to employ the mode of wet-milling.In order to obtain stably dispersing
The molecular sieve pulp for being more suitable for preparing catalyst of the present invention, contain dispersant in preferred molecular sieve slurries.Dispersant can be
Molecular sieve pulp is made to be eventually adding, can also be added during molecular sieve pulp is prepared.Slurry is prepared using wet-milling mode
If liquid, dispersant is preferably added during wet-milling.
In above-mentioned technical proposal, the consumption of dispersant is not particularly limited, in the understanding scope of those skilled in the art
Inside, but preferred dispersants and the weight of molecular sieve ratio are（0.01~20）：100.
In above-mentioned technical proposal, prepare the conventional dispersant of molecular sieve pulp and be used equally for the present invention；But it preferably is selected from molecule
In have one or more in polyhydroxy, the poly- compound for completing acidic group or polyoxyethylene groups；Most preferably from polyethylene glycol, the third three
One or more in alcohol, polyvinyl alcohol or polyacrylic acid.
To solve the three of above-mentioned technical problem, technical scheme is as follows：Polyoxymethylene dimethyl ether synthetic method, with first
Alcohol, dimethoxym ethane and paraformaldehyde are raw material, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 0.1~2.5: 0.01~12.5
: 1, it is 50~200 DEG C in reaction temperature, under conditions of reaction pressure is 0.1~10MPa, the skill of one of raw material and technical problem
Ordered structure catalyst any one of art scheme is contacted, reaction generation polyoxymethylene dimethyl ether.
Methanol in above-mentioned technical proposal: dimethoxym ethane: paraformaldehyde mol ratio is preferably 0.2~1: 0.1~4: 1.Raw material body
Product air speed is preferably 1000~10000hr-1.Reaction temperature is preferably 80~150 DEG C.Reaction pressure is preferably 1~6MPa.
After the present invention, under the conditions of on year-on-year basis, it is only the 10% of traditional catalyst in the selective molecular sieve consumptions of n=3, takes
Beneficial technique effect was obtained, in the industrial production available for polyoxymethylene dimethyl ether catalyst.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of catalyst：
By 24.81 grams (in terms of butt, similarly hereinafter) type ZSM 5 molecular sieve powder (d90=15 microns, Si/Al=150 Nankai is big
Chemical catalyst factory product) mixed with 74.44 grams of deionized waters, wet ball grinding is into molecular sieve pulp, sieve particle diameter d90=6
Micron, (percetage by weight of polyethylene glycol is 0.75 gram of the addition polyethylene glycol PEG400 aqueous solution in solution in slurries
2wt%), the addition of the solution is the 3wt% of molecular sieve, and stirring obtains molecule in coating slurry, coating slurry in 25 minutes
Sieve content is 24.81wt%.
By 1 liter of honeycomb substrate (cordierite honeycomb carrier, diameter 5CM, long 5CM, per square inch the duct number on cross section
400cpsi) mixed with 2 liters of coating slurries, be that 10 meter per second normal temperature (25 DEG C) air purging carrier duct is removed for 15 minutes with flow velocity
The coating slurry of flowing, is calcined 2 hours at 120 DEG C at drying 4 hours, 650 DEG C, obtains the honeybee with molecular sieve catalyst coating
Nest structure catalyst.Wherein, in catalyst, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 2】
The preparation of catalyst：
For MCM-56 (Si/Al=100) outside, his process is same as Example 1 for removing coating active component.Wherein, catalyst
In, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 3】
The preparation of catalyst：
For β zeolites (Si/Al=150) outside, other processes are same as Example 1 for removing coating active component.Wherein, catalyst
In, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 4】
The preparation of catalyst：
For MCM-22 (Si/Al=150) outside, other processes are same as Example 1 for removing coating active component.Wherein, catalyst
In, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 5】
The preparation of catalyst：
It is same as Example 1.
Evaluating catalyst：
Fix 200 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 6】
The preparation of catalyst：
For MCM-56 (Si/Al=100) outside, other processes are same as Example 1 for removing coating active component.Wherein, catalyst
In, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 180 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 7】
The preparation of catalyst：
It is same as Example 1.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 5MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 8】
The preparation of catalyst：
It is same as Example 1.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 4: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 9】
The preparation of catalyst：
It is same as Example 1.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 1000hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 10】
The preparation of catalyst：
For ZSM-5 (Si/Al=100) outside, other processes are same as Example 1 for removing coating active component.Wherein, catalyst
In, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Embodiment 11】
The preparation of catalyst：
By 12.40 grams (in terms of butt, similarly hereinafter) type ZSM 5 molecular sieve powder (d90=15 microns, Si/Al=150 Nankai is big
Chemical catalyst factory product), 12.40 grams of MCM-56 (Si/Al=100) mix with 74.44 grams of deionized waters, and wet ball grinding is into molecule
Screening the pulp liquid, d90=6 microns of sieve particle diameter adds 0.75 gram of the polyethylene glycol PEG400 aqueous solution (in solution in slurries
The percetage by weight of polyethylene glycol is 2wt%), the addition of the solution is the 3wt% of molecular sieve, and stirring is applied for 25 minutes
Molecular sieve content is 24.75wt% in layer slurries, coating slurry.
By 1 liter of honeycomb substrate (cordierite honeycomb carrier, diameter 5CM, long 5CM, per square inch the duct number on cross section
400cpsi) mixed with 2 liters of coating slurries, be that 10 meter per second normal temperature (25 DEG C) air purging carrier duct is removed for 15 minutes with flow velocity
The coating slurry of flowing, is calcined 2 hours at 120 DEG C at drying 4 hours, 650 DEG C, obtains the honeybee with molecular sieve catalyst coating
Nest structure catalyst.Wherein, in catalyst, skeleton carrier is 92wt%, and coating is 8wt%, and coating layer thickness is 10 microns.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
【Comparative example 1】
The preparation of molecular sieve catalyst：Using ZSM-5 molecular sieve（Si/Al=150）150g, with 30g adhesives intend thin water aluminium
Stone is mixed with above-mentioned molecular sieve, adds 3g sesbania powder extrusion aids, is molded on F-26 type double screw banded extruders, and 450 DEG C of roastings 2 are small
When, a diameter of 5CM is made, length is 5CM, per square inch the cylindrical type molecular sieve of the duct number 400cpsi on cross section.Its
Middle molecular sieve content 80wt%.
Evaluating catalyst：
Fix 100 milliliters of catalyst obtained by above-mentioned preparations in 500 milliliters of fixed bed reactors, with methanol, dimethoxym ethane with it is many
Polyformaldehyde is raw material, raw material volume air speed 2500hr-1, wherein methanol: dimethoxym ethane: paraformaldehyde mol ratio is 1: 2: 1, in reaction
Temperature is 150 DEG C, and reaction pressure is under conditions of 2MPa, reaction samples, and through gas chromatographic analysis, is included in sample after 4 hours
Polyoxymethylene dimethyl ether and unreacted raw material, it constitutes distribution such as table 1.
Table 1
Claims (6)
1. polyoxymethylene dimethyl ether synthetic method, using fixed-bed process, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein
Methanol: dimethoxym ethane: paraformaldehyde mol ratio is 0.1~2.5: 0.01~12.5: 1, is 50~200 DEG C in reaction temperature, reaction
Pressure is under conditions of 0.1~10MPa, raw material contacts with ordered structure catalyst, and reaction generation polyoxymethylene dimethyl ether is described
Ordered structure catalyst is made up of skeleton carrier and molecular sieve coating, and the molecular sieve coating is selected from beta-zeolite molecular sieve, MCM-22
Or at least one in MCM-56 zeolite molecular sieves, described ordered structure catalyst middle skeleton carrier accounts for 60~99wt%, point
Son sieve coating accounts for 1~40wt%, and the preparation of the ordered structure catalyst comprises the following steps：
(1) required molecular sieve is distributed to the molecular sieve pulp for being made that sieve particle d 90 is 1~30 micron in water；
(2) slurries obtained with step (1) coat the skeleton carrier；
(3) dry, roasting obtains the catalyst.
2. synthetic method according to claim 1, it is characterized in that the coating layer thickness is 5~100 microns.
3. synthetic method according to claim 1, it is characterized in that the molecular sieve pulp of step (1) system by the way of wet-milling
It is standby.
4. synthetic method according to claim 3, it is characterized in that adding dispersant during the wet-milling of step (1).
5. synthetic method according to claim 1, it is characterized in that being added in the molecular sieve pulp that step (1) is obtained scattered
Agent.
6. the synthetic method according to claim 4 or 5, it is characterized in that the dispersant has polyhydroxy in molecule, gathered
One or more in the compound of carboxylic acid group or polyoxyethylene groups.
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| 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 |
| CN103285905A (en) * | 2012-02-29 | 2013-09-11 | 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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| CN102000559B (en) * | 2010-11-18 | 2012-06-27 | 中国海洋石油总公司 | Method for preparing dimethoxymethane by adopting supported niobium oxide catalyst |
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| 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 |
| CN103285905A (en) * | 2012-02-29 | 2013-09-11 | 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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| Disproportionation of Toluene on ZSM5 Washcoated Monoliths;B. Mitra et al;《AIChE Journal》;20111231;第57卷(第12期);3480-3495 * |
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