CN104292084B - High silica alumina ratio molecular sieve catalytic prepares the method for polyoxymethylene dimethyl ether - Google Patents
High silica alumina ratio molecular sieve catalytic prepares the method for polyoxymethylene dimethyl ether Download PDFInfo
- Publication number
- CN104292084B CN104292084B CN201410449226.XA CN201410449226A CN104292084B CN 104292084 B CN104292084 B CN 104292084B CN 201410449226 A CN201410449226 A CN 201410449226A CN 104292084 B CN104292084 B CN 104292084B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- dimethyl ether
- reaction
- methylal
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method that high silica alumina ratio molecular sieve catalytic prepares polyoxymethylene dimethyl ether is for raw material with methylal and trioxymethylene, be 60-200 DEG C in temperature of reaction, reaction times is under 0.2-48h condition, raw material and hydrogen type molecular sieve catalyzer under stirring contact reacts generate polyoxymethylene dimethyl ether, after reaction terminates, by centrifugal mode separating catalyst and liquid product, wherein reactant methylal and trioxymethylene mol ratio are 1-5, and catalyst levels is the 1-10wt% of total reactant.It is easy that the present invention has separation, consumes energy low, non-corrosiveness, the advantage that target product selectivity is high, catalyzer repeating utilization factor is high.
Description
Technical field
The invention belongs to a kind of preparation method of polymethoxy dimethyl ether, particularly relate to polyoxymethylene dimethyl ether prepared by high silica alumina ratio molecular sieve method as effective catalyst.
Background technology
Polyoxymethylene dimethyl ether (PODE
n ) be the general designation of a class polyether material, chemical formula is CH
3(CH
2o)
n oCH
3, (n>1), oligopolymer is the flammable liquid that a kind of achromaticity and clarification has pungent odour.PODE
n there is higher oxygen level (42%-51%) and cetane value (>60), especially PODE
2-8, because it is with the physicals extremely close with diesel oil, adds in right amount in diesel oil and can improve diesel oil combustion position within the engine, improve thermo-efficiency, significantly reduce the discharge of nitrogen oxide in tail gas and carbon monoxide, and PODE
2-8as diesel-dope without the need to doing any change to existing engine apparatus, it is the diesel-dope being acknowledged as the most value of environmental protection at present.And for reaction raw materials methylal and trioxymethylene, all by methanol conversion.In view of coal-based methanol technology is quite ripe, preparation PODE
2-8, can be considered the further extension of methyl alcohol downstream industry chain, contribute to reducing the dependence to petroleum resources, therefore, exploitation PODE
n product has good strategic value, to Economic development and environment protection all significant.
EP1505049 describes the example that a methyl alcohol and paraformaldehyde prepare polyoxymethylene dimethyl ether under the effect of trifluoromethanesulfonic acid, and formaldehyde and methanol molar ratio are 1.3, methyl alcohol and H
+mol ratio is 940, and temperature of reaction and time are respectively 115
oc and 20min, obtains PODE
2-5selectivity be 43.2%; BASF AG reports in patent US7999140B2, and employing sulfuric acid is catalyzer, and dme and trioxymethylene are raw material, and product is separated by catalytic distillation column, and reaction 8h reaches balance, PODE in product
2-4massfraction be 92%; But this complex technical process, cost is too high.US2449469 and US5746785 individually disclose a kind of with methylal and paraformaldehyde for raw material, with sulfuric acid and formic acid for catalyzer, prepare the method for polyoxymethylene dimethyl ether series product.Liquid acid catalyst is with low cost, but there is the serious problem of catalytic erosion, and environmental pollution is large, and catalyzer and product are difficult to the problem that is separated.
It is catalyzer with ionic liquid that CN101182367 discloses a kind of, and with methyl alcohol and trioxymethylene for the method for polyoxymethylene dimethyl ether prepared by raw material, temperature of reaction is 60-120 DEG C, PODE
3-8selectivity can reach 43.7%.It is high that ionic liquid has catalytic efficiency as catalyzer, and corrodibility is low, but ionic liquid exists the not high and Separation and Recovery of catalyzer self of selectivity and the problem of purification.
Although can obtain target product PODEn using sulfuric acid, trifluoromethanesulfonic acid, formic acid and ionic liquid etc. as catalyzer, the catalyzer existed in PODEn production technique has the problems such as corrodibility, product separating technique is complicated, selectivity is low also to be needed to research and solve further.
CN101768058B discloses and adopts with methyl alcohol and trioxymethylene for raw material, and catalyzer is selected from the method as catalyst preparing polyoxymethylene dimethyl ether such as β zeolite, ZSM-5, MCM-22, MCM-56 zeolite molecular sieve.Wherein, in 300 milliliters of tank reactors, add 2 grams of catalyzer HY, 100 ml methanol and 100 grams of trioxymethylenes, nitrogen purging also keeps 1MPa pressure, is heated to 150 DEG C and stirs 4 hours, filtering separation catalyzer and liquid composition, through gas chromatographic analysis, PODE in component
2-10account for 62.5% of component concentration.
CN103664549A discloses with methyl alcohol, methylal and paraformaldehyde as raw material, reaction generates polyoxymethylene dimethyl ether, catalyst levels is 0.1 ~ 5.0% of raw material weight, catalyzer used with the one in SBA-15, MCM-41 or MCM-22 molecular sieve for carrier, SO
4 2-/ ZrO
2, SO
4 2-/ Fe
2o
3, Cl
-/ TiO
2or Cl
-/ Fe
2o
3in a kind of solid acid be active ingredient;
CN103880612A by with methyl alcohol, methylal and paraformaldehyde for raw material, what catalyzer was selected from least one in P/HZSM-5, Mg/HZSM-5, Al/HZSM-5, Zn/HZSM-5, Cu-P/HZSM-5, Zn-P/HZSM-5, P/SBA-15, Mo/SBA-15 or Mo-P/SBA-15 has synthesized polyoxymethylene dimethyl ether.
Many disadvantageous effects can be brought as the generation that the defect of initial feed is water in reaction process by methyl alcohol, difficulty and the energy consumption of product separation can be increased, reduce per pass conversion, and make the PODEn hydrolysis formed form unstable hemiacetal in the presence of acidic, the hemiacetal of this instability reduces the flash-point of diesel fuel mixtures, damages its quality.And due to hemiacetal close with acetal boiling point, be difficult to remove in PODEn.
CN103420815A reports a kind of synthetic method of polyoxymethylene dimethyl ether, with methylal and trioxymethylene for raw material, methylal: the mol ratio of trioxymethylene is 0.5 ~ 10: 1, it is 70 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.2 ~ 6MPa condition, raw material and catalyzer generation catalyzed reaction obtain polyoxymethylene dimethyl ether, catalyst levels is 0.1 ~ 5.0% of raw material weight, catalyzer wherein used comprises following component with weight parts: a) carrier of 30 ~ 80 parts, and carrier is selected from least one in SBA-15, MCM-41, MCM-22 molecular sieve; With carry b thereon) 20 ~ 70 parts be selected from SO
4 2-/ ZrO
2, SO
4 2-/ Fe
2o
3, Cl
-/ TiO
2or Cl
-/ Fe
2o
3in at least one solid super-strong acid.
Take molecular sieve as carrier, superpower solid acid is that active ingredient catalyzes and synthesizes polyoxymethylene dimethyl ether, can improve the selectivity of target product, is separated relatively easy.But super acids is easy to run off as active ingredient, and catalyzer repeating utilization factor is not high.
It is catalyzer that CN102040491 describes solid molecular sieves, and methyl alcohol, methylal and paraformaldehyde are urged as raw material, synthesizing polyoxymethylene dme.Use methyl alcohol does the generation that raw material can cause hemiacetal in product, and then causes the decline of target product performance.Paraformaldehyde is cheap, replaces the trioxymethylene in traditional raw material, reduces raw materials cost to a certain extent, but uses paraformaldehyde to do raw material, and target product selectivity can reduce, and by product is many.Partial reaction process improves pressure simultaneously, adds the complicacy of reaction.And this invention is only introduced part low silica-alumina ratio molecular sieve catalytic performance, the detailed effect of hydrogen type molecular sieve to this reaction is not fully described out.
Summary of the invention
For Problems existing in existing polyoxymethylene dimethyl ether production technology, the object of this invention is to provide a kind of catalyzer is separated easier with reaction product, consume energy low, non-corrosiveness, the preparation method of the polyoxymethylene dimethyl ether that reaction process is anhydrous and hemiacetal generates, target product selectivity is high, catalyzer repeating utilization factor is high.
For reaching above-mentioned purpose, the present invention only adopts methylal and trioxymethylene as reaction raw materials, guarantees the generation not having hemiacetal and water in reaction product, can ensure that the performance of target product, again reduce the energy consumption of sepn process.Without the need to any pressure exerting device in reaction process, higher yields can be obtained by means of only reaction pressure itself.For thoroughly probing into the performance of molecular sieve catalyst, the present invention is by a large amount of catalyst preparing, active appraisal experiment and com-parison and analysis, and successfully develop a kind of highly active catalyzer, i.e. high silica alumina ratio molecular sieve, wherein silica alumina ratio is between 200 to 900.In this catalyst reaction process, target product mass yield reaches as high as 77.4%, and the basic no coupling product of this process generates, and only needs a small amount of raw material in reaction gained mixture to be separated, and just can obtain the polyoxymethylene dimethyl ether of higher degree.Simultaneously, by carrying out repeatedly replica test to active best molecular sieve catalyst, this process is without the need to any activated measure, after centrifugation catalyzer and reaction mixture, gained catalyzer is directly used in and tests next time, find that this catalyst performance is extremely stable, process of the present invention has carried out detailed discussion to molecular sieve, find that high silica alumina ratio molecular sieve activity is higher, more stable, preparation process is simple.The present invention greatly reduces industrial cost and energy consumption, has larger industrialization potential.
The present invention prepares the technique of polyoxymethylene dimethyl ether, specifically comprises the steps:
(1) fresh sodium form molecular sieve is exchanged by 1-3mol/L ammonium chloride or ammonium nitrate solution, 60-80
oexchange twice under C, each 3-6 hour, obtains hydrogen type molecular sieve;
(2) with methylal and trioxymethylene for raw material, be 60-200 DEG C in temperature of reaction, reaction times is under 0.2-48h condition, raw material and catalyzer under stirring contact reacts generate polyoxymethylene dimethyl ether, after reaction terminates, by centrifugal mode separating catalyst and liquid product, wherein reactant methylal and trioxymethylene mol ratio are 1-5, and catalyst levels is the 1-10wt% of total reactant.
Sodium form molecular sieve as above is the one in ZSM-5, MCM-41, ZSM-48, SBA-15, and silica alumina ratio is not less than 200.
Reactant methylal as above described and the best scope of trioxymethylene mol ratio are 1.5-3.
Temperature of reaction as above is preferably 120-160 DEG C.0.75-10h is preferably between seasonable.
Sodium form molecular sieve as above is the one in ZSM-5, MCM-41, ZSM-48, SBA-15, and silica alumina ratio is preferably between being greater than between 200 to 900.
Described catalyst levels is preferably the 1-5wt% of total reactant.
Studied the effect of hydrogen type molecular sieve in the present invention in great detail, found that the molecular sieve of low silica-alumina ratio easily causes the generation of methyl-formiate, when silica alumina ratio higher than 200 time, by product disappears substantially, and product mainly concentrates on PODE
2-8, by analysis and characterization, find that non-framework aluminum easily causes the generation of byproduct formic acid methyl esters, framework aluminum is more prone to generate PODEn.Non-framework aluminum corresponding L acid acidic site, framework aluminum corresponding B acid acidic site, that is B acid is more conducive to the generation of PODEn.And the molecular sieve of high silica alumina ratio meets this condition just, framework aluminum, B acid site.Therefore high silica alumina ratio molecular sieve has best catalytic performance.Meanwhile, in reaction evaluating process, investigate the impact in reaction times, found for high silica alumina ratio catalyzer, only need 45min to reach chemical equilibrium.Describe compared to the reaction in CN103420815A, CN103880612A and CN102040491, the reaction times of the present invention is shorter, consumes energy lower.
The invention provides a kind of cheap, there is the molecular sieve catalyst of superior catalytic methylal and trioxymethylene, solve with methyl alcohol be generate by product hemiacetal in Material synthesis polyoxymethylene dimethyl ether process and energy consumption of reaction high, the problem that target product yield is low.The molecular sieve catalyst of the present invention's exploitation meets following condition: (1), under the lower pressure of about 1MPa, catalyzer has higher activity; (2) catalyzer reusability is high, without the need to pre-treatment, can ensure the continuity that live catalyst supplements in industrial production; (3) catalyzer has higher physical strength, meets the requirement of constantly stirring; (4) catalyzer has excellent settling property, makes to obtain catalyzer easily and liquid phase separation.
Embodiment
Embodiment 1
Choose 5gNaZSM-48 (Si/Al=220) molecular sieve and be placed in round-bottomed flask, add the deionized water of 150ml subsequently, 8g ammonium chloride, is heated to 80 in water-bath
oc also constantly stirs 4h, centrifuging, after obtaining molecular sieve filter cake, repeats above-mentioned steps once.Finally by gained molecular sieve 110
othe dry 12h of C, grinding, 550
oc roasting 10h, obtains hydrogen type molecular sieve;
0.83g catalyzer HZSM-48 (Si/Al=220) is added in 100ml tank reactor, 7.6g methylal and 9.0g trioxymethylene, be heated to 120 DEG C and stir 0.75h, centrifugation catalyzer and reaction product, collect liquid product, add internal standard substance and carry out gas chromatographic analysis, product comprises unreacted methylal and trioxymethylene, product composition distribution following (representing with % by weight): methylal 16.8%, trioxymethylene 3.9%, methyl-formiate 3.2%, PODE
2-8=75.2%.
Embodiment 2
Choose 5gNaZSM-48 (Si/Al=380) molecular sieve and be placed in round-bottomed flask, add the deionized water of 150ml subsequently, 24g ammonium nitrate, is heated to 70 in water-bath
oc also constantly stirs 5h, centrifuging, after obtaining molecular sieve filter cake, repeats above-mentioned steps once.Finally by gained molecular sieve 110
othe dry 12h of C, grinding, 550
oc roasting 10h, obtains hydrogen type molecular sieve;
0.5g catalyzer HZSM-48 (Si/Al=380) is added in 100ml tank reactor, 38g methylal and 9.0g trioxymethylene, be heated to 140 DEG C and stir 6h, centrifugation catalyzer and reaction product, collect liquid product, add internal standard substance and carry out gas chromatographic analysis, product comprises unreacted methylal and trioxymethylene, product composition distribution following (representing with % by weight): methylal 30.2%, trioxymethylene 0.0%, methyl-formiate 3.2%, PODE
2-8=65.3%.
Embodiment 3
Choose 10gNaMCM-41 (Si/Al=400) molecular sieve and be placed in round-bottomed flask, add the deionized water of 300ml subsequently, 16g ammonium chloride, is heated to 80 in water-bath
oc also constantly stirs 4h, centrifuging, after obtaining molecular sieve filter cake, repeats above-mentioned steps once.Finally by gained molecular sieve 110
othe dry 12h of C, grinding, 550
oc roasting 10h, obtains hydrogen type molecular sieve;
0.7g catalyst HM CM-41 (Si/Al=400) is added in 100ml tank reactor, 15.2g methylal and 9.0g trioxymethylene, be heated to 160 DEG C and stir 4h, centrifugation catalyzer and reaction product, collect liquid product, add internal standard substance and carry out gas chromatographic analysis, product comprises unreacted methylal and trioxymethylene, product composition distribution following (representing with % by weight): methylal 20.9%, trioxymethylene 3.8%, methyl-formiate 1.5%, PODE
2-8=72.9%.
Embodiment 4
Choose 10gNaSBA-15 (Si/Al=360) molecular sieve and be placed in round-bottomed flask, add the deionized water of 300ml subsequently, 48g ammonium nitrate, is heated to 70 in water-bath
oc also constantly stirs 5h, centrifuging, after obtaining molecular sieve filter cake, repeats above-mentioned steps once.Finally by gained molecular sieve 110
othe dry 12h of C, grinding, 550
oc roasting 10h, obtains hydrogen type molecular sieve;
1.0g catalyzer HSBA-15 (Si/Al=360) is added in 100ml tank reactor, 15.2g methylal and 9.0g trioxymethylene, be heated to 180 DEG C and stir 1h, centrifugation catalyzer and reaction product, collect liquid product, add internal standard substance and carry out gas chromatographic analysis, product comprises unreacted methylal and trioxymethylene, product composition distribution following (representing with % by weight): methylal 21.8%, trioxymethylene 2.9%, methyl-formiate 2.8%, PODE
2-8=71.6%.
Embodiment 5
Choose 10gNaZSM-5 (Si/Al=280) molecular sieve and be placed in round-bottomed flask, add the deionized water of 300ml subsequently, 16g ammonium chloride, is heated to 80 in water-bath
oc also constantly stirs 4h, centrifuging, after obtaining molecular sieve filter cake, repeats above-mentioned steps once.Finally by gained molecular sieve 110
othe dry 12h of C, grinding, 550
oc roasting 10h, obtains hydrogen type molecular sieve;
0.5g catalyzer HZSM-5 (Si/Al=280) is added in 100ml tank reactor, 15.2g methylal and 9.0g trioxymethylene, be heated to 60 DEG C and stir 48h, centrifugation catalyzer and reaction product, collect liquid product, add internal standard substance and carry out gas chromatographic analysis, product comprises unreacted methylal and trioxymethylene, product composition distribution following (representing with % by weight): methylal 19.2%, trioxymethylene 4.6%, methyl-formiate 0.7%, PODE
2-8=73.5%.
Embodiment 6
Choose 5gNaZSM-5 (Si/Al=340) molecular sieve and be placed in round-bottomed flask, add the deionized water of 150ml subsequently, 24g ammonium nitrate, is heated to 70 in water-bath
oc also constantly stirs 5h, centrifuging, after obtaining molecular sieve filter cake, repeats above-mentioned steps once.Finally by gained molecular sieve 110
othe dry 12h of C, grinding, 550
oc roasting 10h, obtains hydrogen type molecular sieve;
1.0g catalyzer HZSM-5 (Si/Al=340) is added in 100ml tank reactor, 15.2g methylal and 9.0g trioxymethylene, be heated to 90 DEG C and stir 20h, centrifugation catalyzer and reaction product, collect liquid product, add internal standard substance and carry out gas chromatographic analysis, product comprises unreacted methylal and trioxymethylene, product composition distribution following (representing with % by weight): methylal 19.2%, trioxymethylene 5.2%, methyl-formiate 0.8%, PODE
2-8=74.3%.
Embodiment 7
Choose 10gNaZSM-5 (Si/Al=580) molecular sieve and be placed in round-bottomed flask, add the deionized water of 300ml subsequently, 16g ammonium chloride, is heated to 80 in water-bath
oc also constantly stirs 4h, centrifuging, after obtaining molecular sieve filter cake, repeats above-mentioned steps once.Finally by gained molecular sieve 110
othe dry 12h of C, grinding, 550
oc roasting 10h, obtains hydrogen type molecular sieve;
1.2g catalyzer HZSM-5 (Si/Al=580) is added in 100ml tank reactor, 15.2g methylal and 9.0g trioxymethylene, be heated to 120 DEG C and stir 0.75h, centrifugation catalyzer and reaction product, collect liquid product, add internal standard substance and carry out gas chromatographic analysis, product comprises unreacted methylal and trioxymethylene, product composition distribution following (representing with % by weight): methylal 18.0%, trioxymethylene 5.1%, methyl-formiate 0.1%, PODE
2-8=77.4%.Meanwhile, the catalyzer of centrifugation gained is directly used in reaction next time, reaction conditions is constant, successive reaction ten times, PODE
2-8distribution is as subordinate list one.
Embodiment 8
Choose 5gNaZSM-5 (Si/Al=960) molecular sieve and be placed in round-bottomed flask, add the deionized water of 150ml subsequently, 14g ammonium chloride, is heated to 60 in water-bath
oc also constantly stirs 6h, centrifuging, after obtaining molecular sieve filter cake, repeats above-mentioned steps once.Finally by gained molecular sieve 110
othe dry 12h of C, grinding, 550
oc roasting 10h, obtains hydrogen type molecular sieve;
2.4g catalyzer HZSM-5 (Si/Al=960) is added in 100ml tank reactor, 15.2g methylal and 9.0g trioxymethylene, be heated to 200 DEG C and stir 0.2h, centrifugation catalyzer and reaction product, collect liquid product, add internal standard substance and carry out gas chromatographic analysis, product comprises unreacted methylal and trioxymethylene, product composition distribution following (representing with % by weight): methylal 23.7%, trioxymethylene 5.9%, methyl-formiate 0.0%, PODE
2-8=70.2%.
Comparative example 1:
As described in patent CN103420815A, in 100 milliliters of tank reactors, add 2 grams of catalyst S O
4 2-/ ZrO
2/ SBA-15 (wherein solid super-strong acid SO
4 2-/ ZrO
2compare for 20:80, SO with the massfraction of molecular sieve carrier SBA-15
4 2-account for ZrO
2the charge capacity of carrier is 1wt.%), 97.2 milliliters of methylals and 100 grams of trioxymethylenes, react 4h under 130 DEG C and 0.5MPa autogenous pressure, by gas chromatographic analysis after the centrifugation of extraction sample.Polyoxymethylene dimethyl ether and unreacted raw material methylal and trioxymethylene is comprised, its composition distribution following (representing with % by weight): methylal, 18.8% in product; Trioxymethylene, 5.1%; Methyl alcohol, 4.2%; PODE
2-4, 56.7%; PODE
5-10, 10.6%.
Comparative example 2:
In 300 milliliters of tank reactors, add 2 grams of catalyst Z SM-5 (Si/Al=49), 100 ml methanol and 100 grams of paraformaldehydes, under 130 DEG C and 0.5MPa autogenous pressure, react 4h, by gas chromatographic analysis after the centrifugation of extraction sample.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution is as follows: methylal, 21.5%; Paraformaldehyde, 3.2%; Methyl alcohol, 6.5%; PODE
2-4, 50.8%; PODE
5-10, 18.0%.
Make molecular sieve be carrier in comparative example 1, solid super-strong acid is active ingredient, and catalyzer is easily separated, improve target product yield, but its catalyst preparation process is complicated, production cost is high, solid super-strong acid acid ion easily runs off simultaneously, and catalytic performance is unstable, easy inactivation.
Use low silica-alumina ratio molecular sieve as catalyzer in comparative example 2, methyl alcohol and paraformaldehyde are as Material synthesis polyoxymethylene dimethyl ether, and reaction process easily generates hemiacetal, affects product characteristics, and target product selectivity PODE
2-10only up to 68.8%, the embodiment of the present invention 1,2 in contrast, only uses high silica alumina ratio molecular sieve as catalyzer, catalytic activity is stablized, and generate without hemiacetal in process, other by products seldom can be ignored, molecular sieve catalyst can repeatedly use, and target product is more concentrated, PODE
2-8mass yield reach as high as 77.4%.
Subordinate list one
Claims (3)
1. high silica alumina ratio molecular sieve catalytic prepares a method for polyoxymethylene dimethyl ether, it is characterized in that comprising the steps:
(1) fresh sodium form molecular sieve is exchanged by 1-3mol/L ammonium chloride or ammonium nitrate solution, 60-80
oexchange twice under C, each 3-6 hour, obtains hydrogen type molecular sieve;
(2) with methylal and trioxymethylene for raw material, be 60-200 DEG C in temperature of reaction, reaction times is for being more than or equal to 0.75h, under being less than 10h condition, raw material and catalyzer under stirring contact reacts generate polyoxymethylene dimethyl ether, after reaction terminates, by centrifugal mode separating catalyst and liquid product, wherein reactant methylal and trioxymethylene mol ratio are 1.5-3, and catalyst levels is the 1-10wt% of total reactant;
Described sodium form molecular sieve is the one in ZSM-5, MCM-41, ZSM-48, SBA-15, and silica alumina ratio is between being greater than between 200 to 900.
2. a kind of high silica alumina ratio molecular sieve catalytic as claimed in claim 1 prepares the method for polyoxymethylene dimethyl ether, it is characterized in that described temperature of reaction is 120-160 DEG C.
3. a kind of high silica alumina ratio molecular sieve catalytic as claimed in claim 1 prepares the method for polyoxymethylene dimethyl ether, it is characterized in that institute's catalyst levels is the 1-5wt% of total reactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410449226.XA CN104292084B (en) | 2014-09-05 | 2014-09-05 | High silica alumina ratio molecular sieve catalytic prepares the method for polyoxymethylene dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410449226.XA CN104292084B (en) | 2014-09-05 | 2014-09-05 | High silica alumina ratio molecular sieve catalytic prepares the method for polyoxymethylene dimethyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104292084A CN104292084A (en) | 2015-01-21 |
| CN104292084B true CN104292084B (en) | 2016-01-27 |
Family
ID=52312078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410449226.XA Active CN104292084B (en) | 2014-09-05 | 2014-09-05 | High silica alumina ratio molecular sieve catalytic prepares the method for polyoxymethylene dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104292084B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237366A (en) * | 2015-09-06 | 2016-01-13 | 常州大学 | Method of preparing polyformaldehyde dimethyl ether through catalysis of sulfates supported by molecular sieve |
| CN106220481B (en) * | 2016-07-27 | 2018-11-23 | 中国科学院山西煤炭化学研究所 | A kind of technique of continuous production polyoxymethylene dimethyl ether |
| CN106883106A (en) * | 2017-03-29 | 2017-06-23 | 哈尔滨师范大学 | The method of the efficient catalytic synthesis of dimethoxym ethane |
| CN113318757A (en) * | 2021-05-26 | 2021-08-31 | 华东理工大学 | Preparation method and application of spherical mesoporous sulfated zirconia solid acid catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029365A2 (en) * | 1998-11-12 | 2000-05-25 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde |
| CN102211036A (en) * | 2010-04-09 | 2011-10-12 | 上海吴泾化工有限公司 | Modified molecular sieve catalyst, and precursor and preparation method thereof |
| CN103755535A (en) * | 2014-01-03 | 2014-04-30 | 中国科学院山西煤炭化学研究所 | Preparation method of polyformaldehyde dimethyl ether |
-
2014
- 2014-09-05 CN CN201410449226.XA patent/CN104292084B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029365A2 (en) * | 1998-11-12 | 2000-05-25 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde |
| CN102211036A (en) * | 2010-04-09 | 2011-10-12 | 上海吴泾化工有限公司 | Modified molecular sieve catalyst, and precursor and preparation method thereof |
| CN103755535A (en) * | 2014-01-03 | 2014-04-30 | 中国科学院山西煤炭化学研究所 | Preparation method of polyformaldehyde dimethyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104292084A (en) | 2015-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101768057B (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN104292084B (en) | High silica alumina ratio molecular sieve catalytic prepares the method for polyoxymethylene dimethyl ether | |
| CN102295734B (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN103880612B (en) | By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers | |
| CN104151148B (en) | Prepared the method for polyoxymethylene dimethyl ethers by paraformaldehyde | |
| CN104725230A (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| CN103664549B (en) | The synthetic method of polyoxymethylene dimethyl ether | |
| CN103664547B (en) | The method of synthesizing polyoxymethylene dme | |
| CN103739458A (en) | Preparation method of polyoxymethylene dimethyl ethers | |
| CN102295539B (en) | Method for catalytically synthesizing polyformaldehyde dimethyl ether | |
| CN103664543B (en) | The method of polyoxymethylene dimethyl ether is prepared by paraformaldehyde | |
| CN104941680B (en) | Glycerine based solid acid catalyst and its application | |
| CN104151147B (en) | With the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers | |
| CN103772161A (en) | Method for preparing polyoxymethylene dimethyl ethers | |
| CN103420818B (en) | Polyformaldehyde dimethyl ether preparation method | |
| CN107915591B (en) | Method for preparing polyformaldehyde dimethyl ether | |
| CN107915589B (en) | Method for generating polyoxymethylene dimethyl ether | |
| CN107915595B (en) | Method for producing polyoxymethylene dimethyl ethers | |
| CN107915597B (en) | Catalyst for preparing polyformaldehyde dimethyl ether | |
| CN107915604B (en) | Method for generating polyoxymethylene dimethyl ether | |
| CN101550350B (en) | Method of catalyzing sorbitol to synthesize bio-petrol | |
| CN103880613A (en) | Method for preparing polyoxymethylene dimethyl ether | |
| CN109651101B (en) | Synthesis method of polyoxymethylene dimethyl ether | |
| CN103880614B (en) | The synthetic method of polyoxymethylene dimethyl ether | |
| CN103420815B (en) | By the method for methylal and trioxymethylene synthesizing polyoxymethylene dme |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |