CN106582834A - Catalyst for preparation of polyoxymethylene dimethyl ether - Google Patents
Catalyst for preparation of polyoxymethylene dimethyl ether Download PDFInfo
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- CN106582834A CN106582834A CN201510671628.9A CN201510671628A CN106582834A CN 106582834 A CN106582834 A CN 106582834A CN 201510671628 A CN201510671628 A CN 201510671628A CN 106582834 A CN106582834 A CN 106582834A
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- 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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Abstract
The invention relates to a catalyst for preparation of polyoxymethylene dimethyl ether, and mainly solves the problems of low activity and selectivity of catalysts in a polyoxymethylene dimethyl ether synthesis process adopting methanol, methylal and paraformaldehyde as the reaction raw materials in the prior art. According to a technical scheme, the catalyst for preparation of polyoxymethylene dimethyl ether is metal ion modified sulfonic acid type polystyrene cation exchange resin, the sulfonic acid type polystyrene cation exchange resin includes a crosslinked polystyrene skeleton and a sulfonic acid group, and the metal includes at least one of IB group and IIA group elements. The catalyst can be used for the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to be used to prepare the catalyst of polyoxymethylene dimethyl ethers.
Background technology
In recent years, with the industrial revolution affect increasingly deeply and China's distinctive " many coals, few oil, have gas " resource general layout, China's oil resource growing tension, oil supply pressure unprecedentedly increase.It is estimated following 10~20 years, China's oil supply rate only~50%.How the energy crisis for solving China using the coal resources of China's abundant is become as researcher urgent problem.Therefore the attention that new oil product succedaneum is increasingly subject to people is developed by coal-based methanol.
Dimethyl ether is proposed as a kind of procetane earliest, and yet with its own cold starting performance is poor, under room temperature, vapour pressure is high, easily produce vapour lock causes dimethyl ether significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether, i.e. Polyoxymethylene dimethyl ethers (PODE), are the common names of a class material, and its skeleton symbol can be expressed as CH3O(CH2O)nCH3, with higher octane number (>30) with oxygen content (42~51%).When the value of n is 2~10, its physical property, combustibility and diesel oil closely, preferably resolve the defect that dimethyl ether is present as derv fuel blend component.Therefore polyoxymethylene dimethyl ether can be used as new cleaning diesel component, and the addition in diesel oil can improve diesel oil combustion position within the engine up to 30% (v/v), improve the thermal efficiency, reduces particulate matter and CO in tail gasxAnd NOxDischarge.It is reported that, add 5~30% CH3OCH2OCH3NO can be reducedx7~10%, PM of discharge reduces by 5~35%.PODE is synthesized by coal-based methanol and not only can replace part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, reduce harm of the diesel combustion to environment, with important strategic importance and good economic worth.
CN 101048357A (method for preparing polyoxymethylene dimethyl ether) are described using mineral acid, sulfonic acid, heteropoly acid, acid-exchange resin, zeolite, aluminium oxide etc. as catalyst, by dimethoxym ethane and metaformaldehyde for reactant synthesizing polyoxymethylene dimethyl ether method.But all await improving using the conversion ratio and selectivity of existing catalyst.
Cation exchange resin shows good catalytic perfomance, but its acid strength is relatively low as solid acid catalyst in the esterification, etherification reaction in Aquo System.Generally using support type resin is prepared, it is improved activity by increasing acidity of catalyst.Metal-modified resin can be adopted, new acid site is formed on a catalyst, can't by other metal ion exchanged, which solves polyoxymethylene dimethyl ether synthesize in the case of in commercial Application, catalyst keeps highly active and its acidity will not by raw material in the contained metal ion problem that replaces and inactivate.
The content of the invention
One of the technical problem to be solved be prior art with methanol, dimethoxym ethane and paraformaldehyde as reaction raw materials synthesizing polyoxymethylene dimethyl ether technique in there is a problem of that n=2-10 selectivity of product is low, there is provided a kind of new catalyst for preparing polyoxymethylene dimethyl ethers.The catalyst has the advantages that the selectivity of product of n=2-10 is high.
The two of the technical problem to be solved are to provide a kind of synthetic method of one of the employing above-mentioned technical problem polyoxymethylene dimethyl ether of the catalyst.
In order to solve one of above-mentioned technical problem, technical scheme is as follows:
For preparing the catalyst of polyoxymethylene dimethyl ethers, the catalyst is metal ion-modified sulfonic acid polystyrene cation exchange resin, and the sulfonic acid polystyrene cation exchange resin includes crosslinked polystyrene skeleton and sulfonic acid group;The metal includes at least one in IB races element and Group IIA element.
In above-mentioned technical proposal, preferably, the preferred Cu of IB races element, the preferred Mg of the Group IIA element.
In above-mentioned technical proposal, the content of metal described in catalyst is preferably greater than 0 and is less than or equal to 10w%.
In above-mentioned technical proposal, the CEC of the resin is preferably 3.0~5.0mmol/g.The exchange capacity is in terms of butt resin.
In above-mentioned technical proposal, the resin can be gel-type or macroporous type.
In above-mentioned technical proposal, the modified metal most preferably includes Cu and Mg simultaneously, and two kinds of metals have synergism in terms of the selectivity to the PODE of n=2~10 is improved.
In order to solve the two of above-mentioned technical problem, technical scheme is as follows:
The synthetic method of polyoxymethylene dimethyl ethers, with methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, methanol can not be 0 with the consumption of dimethoxym ethane simultaneously, raw material is contacted with catalyst described above, and reaction generates polyoxymethylene dimethyl ether.
In above-mentioned technical proposal, catalyst amount is preferably the 0.05~10% of raw material weight;More preferably the 0.1~5% of raw material weight.
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, the response time is preferably 1 to 20 hour, more 4 to 12 hours.
In above-mentioned technical proposal, in raw material, methanol is preferably (0.4~5) with the mass ratio of paraformaldehyde with the consumption sum of dimethoxym ethane: 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, and may be referred to ion-exchange process commonly used in the prior art and is prepared.Following steps are may include for example:Sulfonic acid sodium form polystyrol cation exchange resin deionized water is washed till after outflow clear water, 1~12h is soaked with 0.5~20% strong acid (such as hydrochloric acid or sulphuric acid), deionized water or alcohol solution dipping soak 1~12h, it is washed with deionized to pH=6 afterwards, that is, obtains sulfonic acid polystyrene cation exchange resin of the present invention.When sulfonic acid polystyrene cation exchange resin of the present invention, rather than sulfonic acid sodium form can also be directly obtained from commercially available channel, may be used to the preparation of catalyst of the present invention.With at least one precursor compound in Cu and Mg, deionized water or ethanol solution are configured to the solution of variable concentrations, carry out ion-exchange treatment with ion exchange resin of the present invention, are finally washed with deionized, it is dried, that is, catalyst of the present invention is obtained.
Using the catalyst of the present invention, the PODE yields of n=2~10 are good, and n=2~10 selectivity of product is up to 86.3%, achieves preferable technique effect.
Heretofore described CEC is in terms of butt resin.
Below by embodiment, the present invention is further elaborated, and the degree of polymerization of the raw material paraformaldehyde adopted in embodiment and comparative example is 5, and selectivity of product is calculated with the polyoxymethylene dimethyl ether that the degree of polymerization is 2~10 as target product on the basis of paraformaldehyde.
Specific embodiment
【Embodiment 1】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the CuCl that Cu is 2 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 2】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the MgCl that Mg is 2 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Mg contents for 2w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 3】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.Take the sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin and be 1 gram containing Mg with 300ml and mix containing the magnesium chloride copper chloride mixed aqueous solution that Cu is 1 gram, 24 hours are stood under room temperature, finally it is washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, the catalyst that Mg contents are that 1w%, Cu content is 1w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 4】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 95 grams of butt resin is taken with 300ml containing the CuCl that Cu is 5 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 5w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 5】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the CuCl that Cu is 2 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 110 DEG C and 0.8MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 6】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the CuCl that Cu is 2 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 150 DEG C and 0.5MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 7】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 95 grams of butt resin is taken with 300ml containing the MgCl that Mg is 5 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Mg contents for 5w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.6MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 8】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the MgCl that Mg is 2 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Mg contents for 2w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 110 DEG C and 0.5MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 9】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the CuCl that Cu is 2 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% is obtained.
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, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 10】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the CuCl that Cu is 2 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
5 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Embodiment 11】
1st, the preparation of catalyst
7320 deionized water of sulfonic acid sodium form polystyrol cation exchange resin is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized to pH=6 afterwards, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the MgCl that Mg is 2 grams2Aqueous solution, stands 24 hours under room temperature, is finally washed with deionized to existing without chloride ion, in vacuum drying oven drying to constant weight, that is, catalyst of the Mg contents for 2w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 110 DEG C and 2MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde are included in product, its composition distribution such as table 1.
【Comparative example 1】
For embodiment 1 in proportion, the catalyst that adopts is differed only in be dried 2 grams of sulfonic acid polystyrene cation exchange resin described in embodiment 1, other process conditions are same as Example 1, the results are shown in Table 1.
Table 1
N is the degree of polymerization, and product is CH3O(CH2O)nCH3。
Claims (9)
1. it is used for preparing the catalyst of polyoxymethylene dimethyl ethers, the catalyst is metal ion-modified sulfonic acid type polyphenyl second
Alkene cation exchange resin, the sulfonic acid polystyrene cation exchange resin include crosslinked polystyrene skeleton and sulfonic group
Group;The metal includes at least one in IB races element and Group IIA element.
2. catalyst according to claim 1, is characterized in that the content of modified metal in catalyst is more than 0 and little
In equal to 10w%.
3. catalyst according to claim 1, is characterized in that the CEC of the resin is 3.0~5.0mmol/
g。
4. catalyst according to claim 1, is characterized in that the resin for gel-type or macroporous type.
5. the synthetic method of polyoxymethylene dimethyl ethers, with methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: first
Acetal: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, methanol can not be 0 with the consumption of dimethoxym ethane simultaneously,
Raw material is contacted with catalyst described in claim 1, and reaction generates polyoxymethylene dimethyl ether.
6. synthetic method according to claim 5, it is characterised in that catalyst amount for raw material weight 0.05~10%.
7. synthetic method according to claim 5, it is characterised in that reaction temperature is 70~200 DEG C.
8. synthetic method according to claim 5, it is characterised in that reaction pressure is 0.2~6MPa.
9. synthetic method according to claim 5, it is characterised in that the response time is 1 to 20 hour.
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