CN106582861B - Polyoxymethylene dimethyl ethers catalyst and preparation method thereof - Google Patents
Polyoxymethylene dimethyl ethers catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to polyoxymethylene dimethyl ethers catalyst and preparation method thereof, mainly solve the problems, such as the prior art using methanol, dimethoxym ethane and paraformaldehyde as that there are catalyst activities in reaction raw materials synthesizing polyoxymethylene dimethyl ether technique is low, selectivity is low, by using polyoxymethylene dimethyl ether catalyst, the catalyst is sulfonic acid polystyrene cation exchange resin and the ferritic hybrid material of permanent magnetism, and the sulfonic acid polystyrene cation exchange resin includes crosslinked polystyrene skeleton and sulfonic acid group；The permanent magnetism ferrite is selected from Eu3Fe5O12、Gd3Fe5O12And Tb3Fe5O12At least one of technical solution, preferably solve the problems, such as this, can be used in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to polyoxymethylene dimethyl ethers catalyst and preparation method thereof.
Background technique
In recent years, as the industrial revolution influences the resource grid goed deep into increasingly and China is distinctive " more coals, have gas at few oil "
Office, China's oil resource growing tension, petroleum supply pressure unprecedentedly increase.It is expected that 10~20 years following, China's oil supply rate
Only~50%.How to be become using the energy crisis that China's coal resources abundant solve China and is badly in need of solving for researcher
Certainly the problem of.Therefore the attention that novel oil product substitute is increasingly subject to people is developed by coal-based methanol.
Dimethyl ether is proposed as a kind of procetane earliest, however since its own cold starting performance is poor, room temperature
Lower vapour pressure is high, is easy to produce vapour lock makes dimethyl ether significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether,
That is Polyoxymethylene dimethyl ethers (PODE), is the common name of a substance, and skeleton symbol can be expressed as
CH3O(CH2O)nCH3, octane number (> 30) with higher and oxygen content (42~51%).When the value of n is 2~10, object
Rationality matter, combustibility and diesel oil are very close, preferably resolve dimethyl ether and lack as existing for derv fuel blend component
It falls into.Therefore polyoxymethylene dimethyl ether can be used as novel 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
It puts.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 replace part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, reduce diesel combustion to the danger of environment
Evil has important strategic importance and good economic value.
CN 101048357A (method for preparing polyoxymethylene dimethyl ether) is described using inorganic acid, sulfonic acid, heteropoly acid, acid
Property ion exchange resin, zeolite, aluminium oxide etc. be used as catalyst, be reactant synthesizing polyoxymethylene by dimethoxym ethane and metaformaldehyde
The method of dimethyl ether.But using the conversion ratio of existing catalyst and selectivity all up for improving, and acid-exchange resin
Solvent resistance and mechanical property are also poor.
Summary of the invention
The first technical problem to be solved by the present invention is that the prior art is former for reaction with methanol, dimethoxym ethane and paraformaldehyde
Expect synthesizing polyoxymethylene dimethyl ether technique in there are catalyst reaction low efficiency, metaformaldehyde be the higher problem of cost of material, mention
For a kind of new polyoxymethylene dimethyl ethers catalyst, the catalyst low-temperature activity is high, selectivity is high and catalyst is more suitable for weight
It is multiple to use.
The second technical problem to be solved by the present invention is the preparation side of catalyst described in one of above-mentioned technical problem
Method.
The third technical problem to be solved by the present invention is to provide a kind of using catalyst described in one of above-mentioned technical problem
Polyoxymethylene dimethyl ether synthetic method.
One of in order to solve the above-mentioned technical problem, technical scheme is as follows: polyoxymethylene dimethyl ethers catalyst, institute
Stating catalyst is sulfonic acid polystyrene cation exchange resin and the ferritic hybrid material of permanent magnetism, the sulfonic acid type polyphenyl
Ethylene cation exchange resin includes crosslinked polystyrene skeleton and sulfonic acid group；The permanent magnetism ferrite is selected from
Eu3Fe5O12、Gd3Fe5O12And Tb3Fe5O12At least one of.
In above-mentioned technical proposal, the permanent magnetism ferrite includes at least Eu3Fe5O12And Gd3Fe5O12, two kinds of permanent magnetism iron
Oxysome has synergistic effect in terms of improving to the selectivity of the PODE of n=2~10.
To solve above-mentioned technical problem two, under technical solution of the present invention: the technical solution of one of above-mentioned technical problem
Described in catalyst preparation method, include the following steps:
(1) polymerization and hydridization: under the initiation of radical initiator, styrene, divinylbenzene, the permanent magnetism ferrite
The mixture of powder and aromatic solvent carries out suspension polymerisation in water phase and obtains coccoid product；Continue after being cleaned with ethyl alcohol
Use H2O cleaning, is dried to obtain catalyst precarsor I；
(2) sulfonation: catalyst precarsor I is swollen with 1,2- dichloroethanes, and then sulfonating agent carries out sulfonation again；
Wherein, with the sum of the permanent magnetism ferrite powder, styrene and divinylbenzene three's parts by weight be 100 and with
Weight ratio meter, the permanent magnetism ferrite: (styrene+divinylbenzene) is (30~80): (20~70).
The sulfonating agent be it is commonly used in the prior art those, such as the concentrated sulfuric acid or oleum.
In order to solve the above-mentioned technical problem three, technical scheme is as follows: the synthesis side of polyoxymethylene dimethyl ethers
Method, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0~10): (0
~10): 1, the dosage of methanol and dimethoxym ethane cannot be 0 simultaneously, and raw material is contacted with catalyst described in claim 1, reaction generation
Polyoxymethylene dimethyl ether.
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%.
Catalyst of the present invention can be realized methanol, dimethoxym ethane and paraformaldehyde catalysis reaction synthesizing polyoxymethylene dimethyl ether, take
For the metaformaldehyde in traditional raw material.Using catalyst of the invention, the PODE yield of n=2~10 is good, the choosing of the product of n=2~10
Selecting property is up to 77.1%, achieves preferable technical effect.In addition, the catalyst uses 10 times, catalytic performance is not obvious
Decline.
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 on the basis of paraformaldehyde by target of the polyoxymethylene dimethyl ether that the degree of polymerization is 2~10 produce
Object calculates.
Specific embodiment
[embodiment 1]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Eu of 500 mesh is then added3Fe5O12It 40 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Eu in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 20:80, catalyst
Quality full exchange capacity is 4.10mmol/g, and range granularity is 0.31~1.25mm (> 95w%).
2, the synthesis of polyoxymethylene dimethyl ether
Be added 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 0.6MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
3, catalyst reuses experiment
Catalyst in embodiment 1 is taken out after the completion of reaction, according to the reaction item in embodiment 1 after being dried
Part carries out 9 reuses, extracts after sample is centrifugated by gas chromatographic analysis.In product comprising polyoxymethylene dimethyl ether and
Unreacted material benzenemethanol and paraformaldehyde, to investigate the thermal stability and chemical stability of the catalyst, composition distribution is such as
Table 2.
[embodiment 2]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Gd of 500 mesh is then added3Fe5O12It 40 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Gd in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 20:80, catalyst
Quality full exchange capacity is 4.20mmol/g, and range granularity is 0.32~1.25mm (> 95w%).
2, the synthesis of polyoxymethylene dimethyl ether
Be added 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 0.6MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 3]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Tb of 500 mesh is then added3Fe5O12It 40 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Tb in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 20:80, catalyst
Quality full exchange capacity is 4.30mmol/g, and range granularity is 0.33~1.25mm (> 95w%).
2, the synthesis of polyoxymethylene dimethyl ether
Be added 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 0.8MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 4]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Eu of 500 mesh is then added3Fe5O12It 69 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Eu in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 30:70, catalyst
Quality full exchange capacity is 4.40mmol/g, and range granularity is 0.34~1.25mm (> 95w%).
2, the synthesis of polyoxymethylene dimethyl ether
Be added 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 0.7MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 5]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Eu of 500 mesh is then added3Fe5O12It 107 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Eu in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 40:60, catalyst
Quality full exchange capacity is 4.50mmol/g, and range granularity is 0.35~1.25mm (> 95w%).
2, the synthesis of polyoxymethylene dimethyl ether
Be added 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 0.7MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 6]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Gd of 500 mesh is then added3Fe5O12It 160 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Gd in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 50:50, catalyst
Quality full exchange capacity is 4.16mmol/g, and range granularity is 0.36~1.25mm (> 95w%).
2, the synthesis of polyoxymethylene dimethyl ether
Be added 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 0.7MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 7]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Tb of 500 mesh is then added3Fe5O12It 373 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Tb in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 70:30, catalyst
Quality full exchange capacity is 4.70mmol/g, and range granularity is 0.37~1.25mm (> 95w%).
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
12h is reacted under 2MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyoxymethylene dimethyl ether in product
And unreacted material benzenemethanol and paraformaldehyde, composition are distributed such as table 1.
[embodiment 8]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Eu of 500 mesh is then added3Fe5O12It 40 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Eu in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 20:80, catalyst
Quality full exchange capacity is 4.10mmol/g, and range granularity is 0.31~1.25mm (> 95w%).
2, the synthesis of polyoxymethylene dimethyl ether
Be added 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 4MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyoxymethylene dimethyl ether in product
And unreacted material benzenemethanol and paraformaldehyde, composition are distributed such as table 1.
[embodiment 9]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Eu of 500 mesh is then added3Fe5O12It 40 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Eu in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 20:80, catalyst
Quality full exchange capacity is 4.10mmol/g, and range granularity is 0.31~1.25mm (> 95w%).
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 120 DEG C and
1.5MPa reacting 4h under self-generated pressure, extract after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 10]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Eu of 500 mesh is then added3Fe5O12It 40 grams, stirs evenly, is being added
300 grams of the PVA aqueous solution of 1.0w% reacts 3h at 70 DEG C under then stirring, and 80 DEG C of reaction 1h, 95 DEG C of reaction 45min are obtained
Coccoid product stops stirring, is kept for 95 DEG C and boils bead 30min.It is clear that product in three-necked flask is all poured into water to progress
It washes.Product continues to use H after being cleaned with ethyl alcohol2O cleaning, is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalyst precarsor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Eu in catalyst preparation3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 20:80, catalyst
Quality full exchange capacity is 4.10mmol/g, and range granularity is 0.31~1.25mm (> 95w%).
2, 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 130 DEG C
With react 4h under 0.8MPa self-generated pressure, extract after sample centrifuge separation by gas chromatographic analysis.It include polyformaldehyde two in product
Methyl ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 11]
1, the preparation of catalyst
(1) polymerization and hydridization: at room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 1 gram of BPO and 40 grams of toluene stir evenly, the Eu of 500 mesh is then added3Fe5O1220 grams, Gd3Fe5O1220 grams of stirrings are equal
It is even, at 300 grams of PVA aqueous solution of addition 1.0w%, at 70 DEG C under then stirring, react 3h, 80 DEG C of reaction 1h, 95 DEG C of reactions
45min obtains coccoid product, stops stirring, is kept for 95 DEG C and boils bead 30min.Product in three-necked flask is all poured into
It is cleaned in water.Product continues to use H after being cleaned with ethyl alcohol2O cleaning is placed in 80 DEG C of dry 4h in baking oven and obtains 200 grams of catalysis
Agent precursor I.
(2) sulfonation: room temperature in 400 grams of 1,2- dichloroethanes is added in 200 grams of catalyst precarsor I and is swollen 4h, 100 are added afterwards
Gram purity is the H of 98w%2SO4, stirring 85 DEG C of sustained response 3h of downloading, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtains the catalyst.
The Eu in catalyst preparation3Fe5O12、Gd3Fe5O12Mass fraction ratio with (styrene+divinylbenzene) is 10:
10:80, catalyst quality full exchange capacity are 4.90mmol/g, and range granularity is 0.39~1.25mm (> 95w%).2, poly- first
The synthesis of aldehyde dimethyl ether
Be added 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 0.6MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
It from embodiment 1, embodiment 2 and is the year-on-year of embodiment 11 as can be seen that improving the PODE to n=2~10
Selectivity aspect Eu3Fe5O12And Gd3Fe5O12With synergistic effect.
[comparative example 1]
In proportion for embodiment 1.
1, the synthesis of polyoxymethylene dimethyl ether
According to patent " method for preparing polyoxymethylene dimethyl ether " (published application number: CN 101048357A) the method,
2 grams of catalyst Amberlite IR15 (ROHM AND HAAS, polystyryl cation exchange tree are added in 300 milliliters of tank reactors
Rouge, exchange capacity 4.10mmol/g), 100 grams of methanol and 100 grams of paraformaldehydes are anti-under 130 DEG C and 0.6MPa self-generated pressure
It answers 4 hours, extracts after sample is centrifugated by gas chromatographic analysis.It include polyoxymethylene dimethyl ether and unreacted original in product
Expect that methanol and paraformaldehyde, composition are distributed following (indicating with weight %): dimethoxym ethane 48.2%, methanol 5.1%, poly
Formaldehyde is 2.1%, n=2 23.1%, n=3 12.4%, n=4 5.5%, n=5-10 3.6%, n > 10, and surplus is right
The selectivity of the selectivity of product n=2~10 is 44.6%.
2, catalyst reuses experiment
By the catalyst Amberlite IR15 in comparative example 1, (ROHM AND HAAS, polystyrol cation exchange resin are handed over
Changing capacity is 4.10mmol/g) it takes out after the completion of reaction, 9 are carried out according to the reaction condition in comparative example 1 after being dried
Secondary reuse is extracted after sample is centrifugated by gas chromatographic analysis.It include polyoxymethylene dimethyl ether and unreacted in product
Material benzenemethanol and paraformaldehyde, to investigate the thermal stability and chemical stability of the catalyst, composition distribution such as table 3.
[comparative example 2]
In proportion for embodiment 1.
1, the synthesis of polyoxymethylene dimethyl ether
2 grams of Eu are added in 300 milliliters of tank reactors3Fe5O12, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C
It reacts 4 hours, is extracted after sample is centrifugated by gas chromatographic analysis under 0.6MPa self-generated pressure.It include polyformaldehyde in product
Dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, composition are distributed following (indicating with weight %): dimethoxym ethane is
39.3%, methanol 9.6%, paraformaldehyde 4.9%, n=2 20.8%, n=3 15.2%, n=4 7.1%, n=
5-10 is 3.1%, n > 10, and surplus, the selectivity to the selectivity of product n=2~10 is 46.2%.
2, catalyst reuses experiment
By the catalyst Eu in comparative example 13Fe5O12It takes out after the completion of reaction, according in comparative example 1 after being dried
Reaction condition carry out 9 times reuse, extract sample centrifuge separation after by gas chromatographic analysis.It include polyformaldehyde two in product
Methyl ether and unreacted material benzenemethanol and paraformaldehyde, to investigate the thermal stability and chemical stability of the catalyst, group
At distribution such as table 4.
It is raw material, Eu that methanol, dimethoxym ethane and paraformaldehyde are used in comparative example3Fe5O12As catalyst in equal conditions
Lower selectivity of product is lower.In contrast, the conversion ratio and the selectivity of product n=2~10 of reaction are higher for the embodiment of the present invention 1,
It is 74.5%, and paraformaldehyde content is lower in product.It can obtain and Eu3Fe5O12It is preferably reacted when as catalyst
As a result.
Table 1
N is the degree of polymerization, product CH3O(CH2O)nCH3
Table 2
N is the degree of polymerization, product CH3O(CH2O)nCH3
Table 3
N is the degree of polymerization, product CH3O(CH2O)nCH3
Table 4
N is the degree of polymerization, product CH3O(CH2O)nCH3
Claims (10)
1. polyoxymethylene dimethyl ethers catalyst, the catalyst is sulfonic acid polystyrene cation exchange resin and permanent magnetism iron
The hybrid material of oxysome, the sulfonic acid polystyrene cation exchange resin include crosslinked polystyrene skeleton and sulfonic group
Group；The permanent magnetism ferrite includes at least Eu3Fe5O12And Gd3Fe5O12。
2. the preparation method of catalyst described in claim 1, includes the following steps:
(1) polymerization and hydridization: under the initiation of radical initiator, styrene, divinylbenzene, the permanent magnetism ferrite powder
With the mixture of aromatic solvent, suspension polymerisation is carried out in water phase and obtains coccoid product；Continue to use H after being cleaned with ethyl alcohol2O
Cleaning, is dried to obtain catalyst precarsor I；
(2) sulfonation: catalyst precarsor I is swollen with 1,2- dichloroethanes, and then sulfonating agent carries out sulfonation again；
Wherein, with the sum of the permanent magnetism ferrite powder, styrene and divinylbenzene three's parts by weight for 100 and with weight
Than meter, the permanent magnetism ferrite: (styrene+divinylbenzene) is (30~80): (20~70).
3. the synthetic method of polyoxymethylene dimethyl ethers, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: dimethoxym ethane:
The mass ratio of paraformaldehyde is (0~10): (0~10): 1, the dosage of methanol and dimethoxym ethane cannot be 0 simultaneously, raw material and right
It is required that the 1 catalyst contact, reaction generate polyoxymethylene dimethyl ether.
4. synthetic method according to claim 3, it is characterised in that catalyst amount is the 0.05~10% of raw material weight.
5. synthetic method according to claim 3, it is characterised in that reaction temperature is 70~200 DEG C.
6. synthetic method according to claim 3, it is characterised in that reaction pressure is 0.2~6MPa.
7. synthetic method according to claim 3, it is characterised in that the degree of polymerization of the paraformaldehyde is 2~8.
8. synthetic method according to claim 7, it is characterised in that the degree of polymerization of the paraformaldehyde is 4~6.
9. synthetic method according to claim 3, it is characterised in that the reaction time is 1 to 20 hour.
10. synthetic method according to claim 9, it is characterised in that the reaction time is 4 to 12 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101733152A (en) * | 2008-11-06 | 2010-06-16 | 中国石油化工股份有限公司 | Magnetic cation exchange resin catalyzer and preparation method and application thereof |
| WO2013004626A1 (en) * | 2011-07-06 | 2013-01-10 | Dsm Ip Assets B.V. | Process for preparing acetals and ketals |
| CN103664545A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for synthesizing polyformaldehyde dimethyl ether from methanol, methylal and paraformaldehyde |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101733152A (en) * | 2008-11-06 | 2010-06-16 | 中国石油化工股份有限公司 | Magnetic cation exchange resin catalyzer and preparation method and application thereof |
| WO2013004626A1 (en) * | 2011-07-06 | 2013-01-10 | Dsm Ip Assets B.V. | Process for preparing acetals and ketals |
| CN103664545A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for synthesizing polyformaldehyde dimethyl ether from methanol, methylal and paraformaldehyde |
| 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 |
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