CN107915603A - For polyoxymethylene dimethyl ether synthetic method - Google Patents
For polyoxymethylene dimethyl ether synthetic method Download PDFInfo
- Publication number
- CN107915603A CN107915603A CN201610881511.8A CN201610881511A CN107915603A CN 107915603 A CN107915603 A CN 107915603A CN 201610881511 A CN201610881511 A CN 201610881511A CN 107915603 A CN107915603 A CN 107915603A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- dimethyl ether
- cation exchange
- polyoxymethylene dimethyl
- exchange resin
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to for polyoxymethylene dimethyl ether synthetic method, mainly solve the problems, such as the prior art using methanol and paraformaldehyde as reaction raw materials synthesizing polyoxymethylene dimethyl ether technique in there are catalyst activity it is low, selectivity it is low, by using for polyoxymethylene dimethyl ether synthetic method, using methanol and paraformaldehyde as raw material, raw material is contacted with polyoxymethylene dimethyl ethers catalyst, reaction generation polyoxymethylene dimethyl ether；The catalyst is the sulfonic acid polystyrene cation exchange resin of modified metal ion modification, and the sulfonic acid polystyrene cation exchange resin includes crosslinked polystyrene skeleton and sulfonic acid group；The modified metal includes the technical solution selected from least one of IB and VIIB metal, available in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to for polyoxymethylene dimethyl ether synthetic method.
Background technology
In recent years, with the resource grid that the industrial revolution influences to go deep into increasingly and China is distinctive " more coals, less oil, have gas "
Office, China's oil resource growing tension, oil supply pressure unprecedentedly increase.It is expected that 10~20 years following, China's oil supply rate
Only~50%.The energy crisis that China how is solved using the coal resources of China's abundant is become as researcher urgent need solution
Certainly the problem of.Therefore the attention that new oil product substitute is increasingly subject to people is developed by coal-based methanol.
Dimethyl ether is proposed as a kind of procetane earliest, yet with its own cold starting performance is poor, room temperature
Lower vapour pressure is high, easily produces vapour lock make it that dimethyl ether is significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether,
That is Polyoxymethylene dimethyl ethers (PODE), are the common names of a kind of material, its skeleton symbol can be expressed as
CH3O(CH2O)nCH3, have higher octane number (>And oxygen content (42~51%) 30).When the value of n is 2~10, its thing
Rationality matter, combustibility and diesel oil are very close, preferably resolve dimethyl ether and are lacked as existing for derv fuel blend component
Fall into.Therefore polyoxymethylene dimethyl ether can be as new cleaning diesel component, and the additive amount in diesel oil, can up to 30% (v/v)
To improve the combustion position of diesel oil within the engine, the thermal efficiency is improved, reduces particulate matter and CO in tail gasxAnd NOxRow
Put.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be reducedxDischarging 7~10%, PM reduces by 5~35%.By coal Ji Jia
Alcohol synthesis PODE can not only substitute part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, reduce danger of the diesel combustion to environment
Evil, has important strategic importance and good economic value.
CN 101048357A (method for preparing polyoxymethylene dimethyl ether) are described using inorganic acid, sulfonic acid, heteropoly acid, acid
Property ion exchange resin, zeolite, aluminium oxide etc. are used as catalyst, are reactant synthesizing polyoxymethylene by dimethoxym ethane and metaformaldehyde
The method of dimethyl ether.But using the conversion ratio and selectivity of existing catalyst all up for improving.
Cation exchange resin is shown good as solid acid catalyst in the esterification, etherification reaction in Aquo System
Catalytic perfomance, but its acid strength is relatively low.Generally use prepares support type resin, makes activity by increasing acidity of catalyst
It is improved.Metal-modified resin can be used, new acid site is formed on a catalyst, can't be handed over by other metal ions
Change, which solves in polyoxymethylene dimethyl ether synthesis, catalyst keeps high activity in commercial Application in the case of and it is acid not
The problem of being substituted by metal ion contained in raw material and inactivating.
The content of the invention
The technical problems to be solved by the invention are that the prior art synthesizes poly- first using methanol and paraformaldehyde as reaction raw materials
In aldehyde dimethyl ether technique there are n=2-10 selectivity of product it is low the problem of, there is provided a kind of new polyoxymethylene dimethyl ether that is used for synthesizes
Method.The catalyst has the advantages that the selectivity of product of n=2-10 is high.
One of in order to solve the above-mentioned technical problem, technical scheme is as follows：
For polyoxymethylene dimethyl ether synthetic method, using methanol and paraformaldehyde as raw material, raw material and polyformaldehyde dimethyl
Ether catalyst contacts, reaction generation polyoxymethylene dimethyl ether；The catalyst is the sulfonic acid type polyphenyl second of modified metal ion modification
Alkene cation exchange resin, the sulfonic acid polystyrene cation exchange resin include crosslinked polystyrene skeleton and sulfonic group
Group；The modified metal includes being selected from least one of IB and VIIB metal.
By the metal-modified sulfonic acid polystyrene cation exchange resin of at least one of IB and VIIB, significantly improve
To the selectivity of the PODE of n=2~10.
In above-mentioned technical proposal, the preferred Cu of IB metals.
In above-mentioned technical proposal, the VIIB metals preferably are selected from least one of Mn and Tc.
In above-mentioned technical proposal, preferably, the modified metal preferably includes Cu and VIIB metals, VIIB metals at the same time
Selected from least one of Mn and Tc, Cu and VIIB metals have in terms of improving to the selectivity of the PODE of n=2~10 at this time
Synergistic effect.Ratio between Cu and VIIB metals is not particularly limited, as long as Cu and VIIB metals are present in catalyst at the same time
In can obtain comparable synergy.
As non-restrictive, the mass ratio of Cu and VIIB metals is 0.01~100, within this range further non-limit
Qualitative citing such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,10 etc..
In above-mentioned technical proposal, the modified metal preferably includes Cu, Mn and Tc at the same time, and Mn and Tc is being improved to n at this time
There is synergistic effect in terms of the selectivity of=2~10 PODE.At this time, the ratio between Mn and Tc is not particularly limited, as long as
Mn and Tc is present in catalyst at the same time can obtain comparable synergy.
As non-restrictive, the mass ratio of Mn and Tc are 0.01~100, further non-limiting act within this range
Example such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,10 etc..
In above-mentioned technical proposal, the content of modified metal is not particularly limited in catalyst, such as, but not limited to catalyst
The content of middle modified metal is more than 0 and is less than or equal to 9.5w%.
In above-mentioned technical proposal, the full exchange capacity of the resin is 3.0~5.9mmol/g.
In above-mentioned technical proposal, the resin can be gel-type or macroporous type.
The preparation method of catalyst, is included in catalytic amount any one of the technical solution of one of above-mentioned technical problem
Acid in the presence of, the sulfonic acid polystyrene cation exchange resin and the modified metal-oxide and/or hydrogen-oxygen will be contained
The suspension contact of compound carries out ion exchange.
In above-mentioned technical proposal, the acid is not particularly limited, if can with containing the modified metal-oxide and/or
The salt that hydroxide reacts can be dissolved in solvent used in the suspension can, under this principle such as, but not limited to
At least one of carboxylic acid of hydrochloric acid, nitric acid or C2~C10.
In above-mentioned technical proposal, the carboxylic acid can be hydroxyl substituted carboxylic acid, such as, but not limited to hydroxyacetic acid, lactic acid,
Tartaric acid, citric acid etc..
In above-mentioned technical proposal, the carboxylic acid can be the monoacid of C2~C10, such as, but not limited to acetic acid etc..
In above-mentioned technical proposal, methanol: the mass ratio of paraformaldehyde is preferably (0.01~100): 1, more preferably 0.1~
10, more more preferably 0.2~5.
In above-mentioned technical proposal, catalyst amount is preferably the 0.05~10% of raw material weight, more preferably raw material weight
0.1~5%.
In above-mentioned technical proposal, reaction temperature is preferably 70~200 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 0.2~6MPa.
In above-mentioned technical proposal, when the reaction time is preferably 1 to 20 small, more 4 to 12 it is small when.
In above-mentioned technical proposal, the sum of dosage of methanol and dimethoxym ethane and the mass ratio of paraformaldehyde are preferably in raw material
(0.4~5): 1；Methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0.2~10): (0.5~10): 1.
In the case where the composition of catalyst of the present invention is clear, the preparation of catalyst is not particularly limited, Ke Yican
Ion-exchange process commonly used in the prior art is examined to be prepared.Such as it may include following steps：By sulfonic acid sodium form polystyrene
Cation exchange resin is washed with deionized water to outflow clear water, soaks 1 with 0.5~20% strong acid (such as hydrochloric acid or sulfuric acid)
~12h, soaks 1~12h with deionized water or alcohol solution dipping, is washed with deionized afterwards to pH=6, that is, obtains this hair
The bright sulfonic acid polystyrene cation exchange resin.When sulfonic acid type of the present invention can also be directly obtained from commercially available channel
Polystyrol cation exchange resin, rather than sulfonic acid sodium form, may be used to the preparation of catalyst of the present invention.
Catalyst using the present invention, the PODE yields of n=2~10 are good, and the selectivity of product of n=2~10 is up to 88.4%,
Achieve preferable technique effect.
Heretofore described full exchange capacity is in terms of butt resin.
Below by embodiment, the present invention is further elaborated, the raw material paraformaldehyde used in embodiment and comparative example
The degree of polymerization be 5, selectivity of product be by 2~10 polyoxymethylene dimethyl ether of the degree of polymerization on the basis of paraformaldehyde target production
Thing calculates.
Embodiment
【Embodiment 1】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin is with 300ml containing the Cu (OH) that Cu is 2 grams2Aqueous suspension mixes, and adds 1 drop ice vinegar
Acid, mixing, when standing 24 is small at room temperature, in vacuum drying chamber drying to constant weight, that is, is made the catalyst that Cu contents are 2w%.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 2】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin, with 300ml containing the Mn (OH) that Mn is 2 grams under nitrogen protection2Aqueous suspension mixes, and adds
Enter 1 drop glacial acetic acid, mix, when standing 24 is small at room temperature, in vacuum drying chamber drying to constant weight, that is, it is 2w%'s that Mn contents, which are made,
Catalyst.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 3】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin, with 300ml containing the Tc (OH) that Tc is 2 grams under nitrogen protection2Aqueous suspension mixes, and adds
Enter 1 drop glacial acetic acid, mix, when standing 24 is small at room temperature, in vacuum drying chamber drying to constant weight, that is, it is 2w%'s that Tc contents, which are made,
Catalyst.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 4】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin, the Cu (OH) that it is 1 gram containing Cu with 300ml that nitrogen protection is lower and Mn is 1 gram2And Mn
(OH)2Mix aqueous suspension mixing, add 1 drop glacial acetic acid, mixing, at room temperature stand 24 it is small when, vacuum drying chamber dry to
Constant weight, that is, it is the catalyst that 1w% and Mn contents are 1w% that Cu contents, which are made,.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
Understood on year-on-year basis from embodiment 4 and embodiment 1 and embodiment 2, Cu and Mn are in choosing of the raising to the PODE of n=2~10
There is synergistic effect in terms of selecting property.
【Embodiment 5】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin, the Cu (OH) that it is 1 gram containing Cu with 300ml that nitrogen protection is lower and Tc is 1 gram2And Tc
(OH)2Mix aqueous suspension mixing, add 1 drop glacial acetic acid, mixing, at room temperature stand 24 it is small when, vacuum drying chamber dry to
Constant weight, that is, it is the catalyst that 1w% and Tc contents are 1w% that Cu contents, which are made,.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
Understood on year-on-year basis from embodiment 5 and embodiment 1 and embodiment 3, Cu and Tc are in choosing of the raising to the PODE of n=2~10
There is synergistic effect in terms of selecting property.
【Embodiment 6】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin, nitrogen protection is down 1 gram containing Cu with 300ml, Tc is 0.5 gram and Mn is 0.5 gram
Cu(OH)2、Tc(OH)2With Mn (OH)2Mixing aqueous suspension mixing, adds 1 drop glacial acetic acid, mixes, when standing 24 is small at room temperature,
In vacuum drying chamber drying to constant weight, that is, it is that 1w%, Tc content are that 0.5w% and Mn contents are urging for 0.5w% that Cu contents, which are made,
Agent.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
Understood on year-on-year basis from embodiment 6 and embodiment 4 and embodiment 5, Mn and Tc are in choosing of the raising to the PODE of n=2~10
There is synergistic effect in terms of selecting property.
【Embodiment 7】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin is with 300ml containing the Cu (OH) that Cu is 2 grams2Aqueous suspension mixes, and adds 1 drop ice vinegar
Acid, mixing, when standing 24 is small at room temperature, in vacuum drying chamber drying to constant weight, that is, is made the catalyst that Cu contents are 2w%.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 100 DEG C and
4h is reacted under 0.6MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 8】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin, the Cu (OH) that it is 1.5 grams containing Cu with 300ml that nitrogen protection is lower and Mn is 0.5 gram2With
Mn(OH)2Mixing aqueous suspension mixing, adds 1 drop glacial acetic acid, mixing, when standing 24 is small at room temperature, is dried in vacuum drying chamber
To constant weight, that is, it is the catalyst that 1.5w% and Mn contents are 0.5w% that Cu contents, which are made,.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 90 DEG C and
4h is reacted under 0.2MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 9】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin, the Cu (OH) that it is 1.5 grams containing Cu with 300ml that nitrogen protection is lower and Tc is 0.5 gram2With
Tc(OH)2Mixing aqueous suspension mixing, adds 1 drop glacial acetic acid, mixing, when standing 24 is small at room temperature, is dried in vacuum drying chamber
To constant weight, that is, it is the catalyst that 1.5w% and Tc contents are 0.5w% that Cu contents, which are made,.
2nd, the synthesis of polyoxymethylene dimethyl ether
0.5 gram of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, at 120 DEG C
With react 4h under 0.8MPa self-generated pressures, extract after sample centrifuges by gas chromatographic analysis.Polyformaldehyde two is included in product
Methyl ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 10】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin, nitrogen protection is lower and 300ml containing Cu is 1.5 grams, Tc is 0.25 gram and Mn is 0.25
Gram Cu (OH)2、Tc(OH)2With Mn (OH)2Aqueous suspension mixing is mixed, adds 1 drop glacial acetic acid, mixing, it is small to stand 24 at room temperature
When, in vacuum drying chamber drying to constant weight, that is, it is that 1.5w%, Tc content are that 0.25w% and Mn contents are that Cu contents, which are made,
The catalyst of 0.25w%.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 3 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 110 DEG C and
4h is reacted under 0.3MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 11】
1st, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, the 4w%'s of each 10 times equivalent to 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin of use
Hydrochloric acid, soaks 4h every time, is washed with deionized to eluate and exists without chlorion afterwards, after 60 DEG C dry, that is, obtains sulphur
Acid type polystyrene cation exchange resin, its full exchange capacity are 4.10mmol/g.Take sulphur of 98 grams equivalent to butt resin
Acid type polystyrene cation exchange resin, the Tc (OH) that it is 1 gram containing Tc with 300ml that nitrogen protection is lower and Mn is 1 gram2And Mn
(OH)2Mix aqueous suspension mixing, add 1 drop glacial acetic acid, mixing, at room temperature stand 24 it is small when, vacuum drying chamber dry to
Constant weight, that is, it is the catalyst that 1w% and Mn contents are 1w% that Tc contents, which are made,.
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
Understood on year-on-year basis from embodiment 11 and embodiment 2 and embodiment 3, Mn and Tc are in choosing of the raising to the PODE of n=2~10
There is synergistic effect in terms of selecting property.
【Comparative example 1】
For embodiment 1 in proportion, the catalyst used is differed only in for the drying sulfonic acid type described in embodiment 1 to gather
2 grams of styrene cation exchange resin, other process conditions are same as Example 1, the results are shown in Table 1.
Table 1
N is the degree of polymerization, product CH3O(CH2O)nCH3。
Claims (10)
1. it is used for polyoxymethylene dimethyl ether synthetic method, using methanol and paraformaldehyde as raw material, raw material and polyoxymethylene dimethyl ethers
Catalyst contacts, reaction generation polyoxymethylene dimethyl ether；It is characterized in that the catalyst is the sulfonic acid type of modified metal ion modification
Polystyrol cation exchange resin, the sulfonic acid polystyrene cation exchange resin include crosslinked polystyrene skeleton and
Sulfonic acid group；The modified metal includes being selected from least one of IB and VIIB metal.
2. according to the method described in claim 1, it is characterized in that VIIB metals are selected from least one of Mn and Tc.
3. according to the method described in claim 1, it is characterized in that the content of modified metal is more than 0 and is less than or equal in catalyst
9.5w%.
4. according to the method described in claim 1, it is characterized in that the full exchange capacity of the resin is 3.0~5.9mmol/g.
5. according to the method described in claim 1, it is characterized in that the resin is gel-type or macroporous type.
6. according to the method described in claim 1, it is characterized in that methanol: the mass ratio of paraformaldehyde is (0.01~100): 1.
7. according to the method described in claim 1, it is characterized in that catalyst amount is the 0.05~10% of raw material weight.
8. according to the method described in claim 1, it is characterized in that reaction temperature is 70~200 DEG C.
9. according to the method described in claim 1, it is characterized in that reaction pressure is 0.2~6MPa.
10. according to the method described in claim 1, it is characterized in that when the reaction time is 1 to 20 small.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610881511.8A CN107915603B (en) | 2016-10-09 | 2016-10-09 | Method for synthesizing polyformaldehyde dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610881511.8A CN107915603B (en) | 2016-10-09 | 2016-10-09 | Method for synthesizing polyformaldehyde dimethyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107915603A true CN107915603A (en) | 2018-04-17 |
| CN107915603B CN107915603B (en) | 2020-04-17 |
Family
ID=61892316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610881511.8A Active CN107915603B (en) | 2016-10-09 | 2016-10-09 | Method for synthesizing polyformaldehyde dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107915603B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651098A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The production method of polyoxymethylene dimethyl ether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549443A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether catalyst and application thereof |
| CN104549502A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for synthesis of polyoxymethylene dimethyl ether and application of catalyst |
| CN106582834A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparation of polyoxymethylene dimethyl ether |
-
2016
- 2016-10-09 CN CN201610881511.8A patent/CN107915603B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549443A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether catalyst and application thereof |
| CN104549502A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for synthesis of polyoxymethylene dimethyl ether and application of catalyst |
| CN106582834A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparation of polyoxymethylene dimethyl ether |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651098A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The production method of polyoxymethylene dimethyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107915603B (en) | 2020-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582834A (en) | Catalyst for preparation of polyoxymethylene dimethyl ether | |
| CN106582835A (en) | Polyformaldehyde dimethyl ether synthesis catalyst | |
| CN102247852B (en) | Cu-Fe-Co base catalyst used for synthesizing low carbon alcohol by utilizing synthesis gas as well as preparation method and application thereof in low carbon alcohol synthesizing process by virtue of synthesis gas | |
| CN106582836A (en) | Catalyst for PODE (polyoxymethylene dimethyl ether) | |
| CN106582837A (en) | Catalyst for producing polyoxymethylene dimethyl ether | |
| CN106588595A (en) | Synthetic method of polyoxymethylene dimethyl ethers | |
| CN106582840A (en) | Catalyst used for preparation of polyoxymethylene dimethyl ether | |
| CN107913736A (en) | Catalyst for polyoxymethylene dimethyl ether synthesis | |
| CN107915603A (en) | For polyoxymethylene dimethyl ether synthetic method | |
| CN107915594A (en) | Synthetic method for polyoxymethylene dimethyl ether | |
| CN107915593A (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN107915604A (en) | The generation method of polyoxymethylene dimethyl ethers | |
| CN107915589A (en) | The method of polyoxymethylene dimethyl ethers generation | |
| CN107913733A (en) | The catalyst of polyoxymethylene dimethyl ethers preparation | |
| CN107915601A (en) | The method of synthesizing polyoxymethylene dimethyl ethers | |
| CN107915595A (en) | The method for generating polyoxymethylene dimethyl ethers | |
| CN107915597A (en) | The catalyst prepared for polyoxymethylene dimethyl ether | |
| CN107915607A (en) | The preparation method of polyoxymethylene dimethyl ether | |
| CN107915591A (en) | The method for preparing polyoxymethylene dimethyl ether | |
| CN107915602A (en) | Polyoxymethylene dimethyl ethers catalyst | |
| CN107913734A (en) | Polyoxymethylene dimethyl ether catalyst for preparing | |
| CN107913735A (en) | Polyoxymethylene dimethyl ether production catalyst | |
| CN107915608A (en) | Polyoxymethylene dimethyl ethers synthetic method | |
| CN107915592A (en) | The synthetic method of polyoxymethylene dimethyl ethers | |
| CN107915605A (en) | It is used to prepare the method for polyoxymethylene dimethyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |