CN107913734A - Polyoxymethylene dimethyl ether catalyst for preparing - Google Patents
Polyoxymethylene dimethyl ether catalyst for preparing Download PDFInfo
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- CN107913734A CN107913734A CN201610879655.XA CN201610879655A CN107913734A CN 107913734 A CN107913734 A CN 107913734A CN 201610879655 A CN201610879655 A CN 201610879655A CN 107913734 A CN107913734 A CN 107913734A
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- catalyst
- dimethyl ether
- polyoxymethylene dimethyl
- exchange resin
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- 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
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- 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
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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Abstract
The present invention relates to polyoxymethylene dimethyl ether catalyst for preparing, mainly solve the problems, such as the prior art using methanol, dimethoxym ethane 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 polyoxymethylene dimethyl ether catalyst for preparing, 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 of VIII group element, available in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to polyoxymethylene dimethyl ether catalyst for preparing.
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 first technical problem to be solved by the present invention is that the prior art is former by reaction of methanol, dimethoxym ethane and paraformaldehyde
Expect synthesizing polyoxymethylene dimethyl ether technique in there are n=2-10 selectivity of product it is low the problem of, there is provided a kind of new polyformaldehyde diformazan
The catalyst of base ether preparation.The catalyst has the advantages that the selectivity of product of n=2-10 is high.
The second technical problem to be solved by the present invention is to provide a kind of using one of the above-mentioned technical problem catalyst
Preparation method.
The third technical problem to be solved by the present invention is that the catalyst described in one of above-mentioned technical problem is synthesizing poly- first
Application in aldehyde dimethyl ether.
One of in order to solve the above-mentioned technical problem, technical scheme is as follows：
Polyoxymethylene dimethyl ether catalyst for preparing, the catalyst are the sulfonic acid polystyrene of modified metal ion modification
Cation exchange resin, the sulfonic acid polystyrene cation exchange resin include crosslinked polystyrene skeleton and sulfonic group
Group；The modified metal includes VIII group element.
In above-mentioned technical proposal, preferably, the modified metal further includes Cu, Cu is with VIII group element in raising pair
There is synergistic effect in terms of the selectivity of the PODE of n=2~10.Ratio between Cu and VIII group element is not particularly limited,
As long as Cu and VIII group element are present in catalyst at the same time can obtain comparable synergy.
As non-restrictive, the mass ratio of Cu and VIII group element is 0.01~100, further non-within this range
Limited 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 VIII group element is selected from least one of Fe, Co and Ni.
In above-mentioned technical proposal, more preferably described modified metal includes at least two and Cu in Fe, Co and Ni, this
When above two VIII elements between improve to the selectivity of the PODE of n=2~10 in terms of have synergistic effect.At this time, Ni,
Ratio between Co and Fe is not particularly limited, as long as at least two in Ni, Co and Fe are present in equal energy in catalyst at the same time
Comparable synergy is obtained, such as, but not limited between Co and Ni, between Ni and Fe.
As non-restrictive, the mass ratio between above two VIII elements is 0.01~100, within this range into
One step non-restrictive such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,10 etc..
As most preferred technical solution, the modified metal includes Fe, Co, Ni and Cu at the same time, at this time to n=2~10
The selectivity of PODE reach best.
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 10w%.
In above-mentioned technical proposal, the full exchange capacity of the resin is preferably 3.0~6.0mmol/g.
In above-mentioned technical proposal, the resin can be gel-type or macroporous type.
In order to solve the above-mentioned technical problem two, technical scheme is as follows：
The preparation of polyoxymethylene dimethyl ether catalyst for preparing any one of the technical solution of one of above-mentioned technical problem
Method, is included in the presence of the acid of catalytic amount, by the sulfonic acid polystyrene cation exchange resin and contains the modification
The suspension contact of metal oxide carries out ion exchange.
In above-mentioned technical proposal, the acid is not particularly limited, as long as can be with being reacted containing the modified metal-oxide
Obtained salt can be dissolved in solvent used in the suspension can, be such as, but not limited under this principle hydrochloric acid, nitric acid or
At least one of carboxylic acid of 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..
To solve the three of above-mentioned technical problem, technical solution of the present invention is as follows：
Polyoxymethylene dimethyl ether catalyst for preparing is synthesizing any one of the technical solution of one of above-mentioned technical problem
Application in polyoxymethylene dimethyl ethers.
The synthetic method of polyoxymethylene dimethyl ethers for example can be, 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 at the same time
0, raw material is contacted with catalyst described above, 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%.
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 88.9%,
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 Ni (OH) that Ni 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 Ni 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 Co (OH) that Co 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 Co 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, with 300ml containing the Fe (OH) that Fe 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 Fe 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 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 Ni is 1 gram2And Ni
(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 Ni 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.
【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, the Cu (OH) that it is 1 gram containing Cu with 300ml that nitrogen protection is lower and Co is 1 gram2And Co
(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 Co 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.
【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, the Cu (OH) that it is 1 gram containing Cu with 300ml that nitrogen protection is lower and Fe is 1 gram2And Fe
(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 Fe 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.
【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, nitrogen protection is down 1 gram containing Cu with 300ml, Co is 0.5 gram and Ni is 0.5 gram
Cu(OH)2、Co(OH)2With Ni (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%, Co content are that 0.5w% and Ni 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.
【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, nitrogen protection is down 1 gram containing Cu with 300ml, Co is 0.5 gram and Fe is 0.5 gram
Cu(OH)2、Co(OH)2With Fe (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%, Co content are that 0.5w% and Fe 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.
【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 down 1 gram containing Cu with 300ml, Ni is 0.5 gram and Fe is 0.5 gram
Cu(OH)2、Ni(OH)2With Fe (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%, Ni content are that 0.5w% and Fe 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.
【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, nitrogen protection is lower and 300ml containing Cu is 1 gram, Co is 0.4 gram, Ni is 0.3 gram and Fe
For 0.3 gram of Cu (OH)2、Co(OH)2、Ni(OH)2With Fe (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixes,
When standing 24 is small at room temperature, in vacuum drying chamber drying to constant weight, that is, it is that 1w%, Co content are 0.4w%, Ni that Cu contents, which are made,
Content is the catalyst that 0.3w% and Fe contents are 0.3w%.
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 12】
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 gram, Co is 0.4 gram, Ni is 0.3 gram and Fe
For 0.3 gram of Cu (OH)2、Co(OH)2、Ni(OH)2With Fe (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixes,
When standing 24 is small at room temperature, in vacuum drying chamber drying to constant weight, that is, it is that 1w%, Co content are 0.4w%, Ni that Cu contents, which are made,
Content is the catalyst that 0.3w% and Fe contents are 0.3w%.
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 0.6MPa 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.
【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 (8)
1. polyoxymethylene dimethyl ether catalyst for preparing, the catalyst is positive for the sulfonic acid polystyrene of modified metal ion modification
Ion exchange resin, the sulfonic acid polystyrene cation exchange resin include crosslinked polystyrene skeleton and sulfonic acid group；
The modified metal includes being selected from VIII group element.
2. polyoxymethylene dimethyl ether catalyst for preparing according to claim 1, it is characterized in that the VIII group element be selected from Fe,
At least one of Co and Ni.
3. polyoxymethylene dimethyl ether catalyst for preparing according to claim 1, it is characterized in that modified metal contains in catalyst
Measure more than 0 and to be less than or equal to 10w%.
4. polyoxymethylene dimethyl ether catalyst for preparing according to claim 1, it is characterized in that the full exchange capacity of the resin
For 3.0~6.0mmol/g.
5. polyoxymethylene dimethyl ether catalyst for preparing according to claim 1, it is characterized in that the resin is gel-type or big
Pass.
6. the preparation method of polyoxymethylene dimethyl ether catalyst for preparing, is included in catalyst any one of Claims 1 to 5
In the presence of the acid of amount, by the sulfonic acid polystyrene cation exchange resin and contain the modified metal-oxide and/or institute
The suspension contact for stating modified metal hydroxide carries out ion exchange.
7. preparation method according to claim 6, it is characterized in that the acid is the carboxylic acid of hydrochloric acid, nitric acid or C2~C10
At least one of.
8. polyoxymethylene dimethyl ether catalyst for preparing is in synthesizing polyoxymethylene dimethyl ethers any one of Claims 1 to 5
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