CN106311328B - A method of preparing the catalyst for synthesizing polymethoxy dimethyl ether - Google Patents

A method of preparing the catalyst for synthesizing polymethoxy dimethyl ether Download PDF

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CN106311328B
CN106311328B CN201610662030.8A CN201610662030A CN106311328B CN 106311328 B CN106311328 B CN 106311328B CN 201610662030 A CN201610662030 A CN 201610662030A CN 106311328 B CN106311328 B CN 106311328B
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reaction
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catalyst
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dimethyl ether
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CN106311328A (en
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吴文源
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Jiangsu Success Resin Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08Ion-exchange resins
    • B01J31/10Ion-exchange resins sulfonated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51Spheres
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48Preparation of compounds having groups
    • C07C41/50Preparation of compounds having groups by reactions producing groups
    • C07C41/56Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones

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Abstract

The present invention provides a kind of method for preparing the catalyst for synthesizing polymethoxy dimethyl ether comprising following steps: step 1, in the reactor equipped with speed-adjustable stir device, reflux condenser, water is added and a certain amount of polymeric dispersant obtains aqueous phase solution;Step 2 is added a certain amount of polymerization initiator in styrene, divinylbenzene and methyl acrylate and allyl itaconates monomer solution and aluminium oxide obtains oily phase;The oil-phase solution is added in the aqueous phase solution by step 3, stirs to get suspension polymerisation solution, and is gradually warmed up, is kept the temperature and obtain solid spherical copolymer pellet;The solid spherical copolymer pellet, dichloroethanes and the concentrated sulfuric acid are carried out heating reaction by step 4, and a certain amount of benzene sulfonic acid is added in reaction after a certain period of time;Step 5, heating and thermal insulation reaction, is added a certain amount of polyethylene glycol, steams dichloroethanes, filter, be dried to obtain catalyst.

Description

A method of preparing the catalyst for synthesizing polymethoxy dimethyl ether
Technical field
The present invention relates to the synthesis field of polymethoxy dimethyl ether more particularly to a kind of prepare for synthesizing polymethoxy two The method of the catalyst of methyl ether.
Background technique
Polymethoxy dimethyl ether (Polyoxymethylene dimethyl ethers, abbreviation PODE or DMMn), is one The common name of substance, skeleton symbol can be expressed as CH3O(CH2O)nCH3, octane number with higher is up to 76, and oxygen content reaches 42~51%.When the value of n is 3~8, physical property, combustibility and diesel oil are very close, especially DMM2, DMM3, DMM4 preferably resolve dimethyl ether as derv fuel is thick and component existing for defect.Polymethoxy dimethyl ether is as novel Clean diesel component, can improve the combustion position of diesel oil within the engine, improve the thermal efficiency, reduce the particulate matter in tail gas with And the discharge of COx and NOx.
Polymethoxy dimethyl ether is usually by providing compound such as methanol, dimethoxym ethane, dimethyl ether of sealing end methyl etc. and mentioning For chain growth section-(CH2O)-compound such as formaldehyde, metaformaldehyde, paraformaldehyde reacted under acid catalysis be made. US5,746,785 describe with Bronsted acid (such as formic acid, sulfuric acid and trifluoromethanesulfonic acid) for catalyst, with dimethoxym ethane and paraformaldehyde For the synthesis technology of the polymethoxy dimethyl ether of raw material, this bronsted acid catalyst is although cheap and easy to get, but corrosivity is strong, it is difficult to Separation, environmental pollution is big, and the requirement to equipment is high.
Summary of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of prepare for synthesizing polymethoxy dimethyl ether The method of catalyst, this method preparation catalyst is easily separated, high temperature resistant, high catalytic efficiency.
A method of preparing the catalyst for synthesizing polymethoxy dimethyl ether comprising following steps:
Water and a certain amount of polymerization dispersion is added in the reactor equipped with speed-adjustable stir device, reflux condenser in step 1 Agent obtains aqueous phase solution;
Step 2 is added certain in styrene, divinylbenzene and methyl acrylate and allyl itaconates monomer solution The polymerization initiator and aluminium oxide of amount obtain oily phase;
The oil-phase solution is added in the aqueous phase solution by step 3, stirs to get suspension polymerisation solution, and gradually Heating, heat preservation obtain solid spherical copolymer pellet;
The solid spherical copolymer pellet, dichloroethanes and the concentrated sulfuric acid are carried out heating reaction, solid spherical by step 4 Copolymer pellet: dichloroethanes: the concentrated sulfuric acid be the proportion of three kinds of components be by weight be 0.1~0.3:0.01~0.03: 0.05~2, a certain amount of benzene sulfonic acid is added in reaction after a certain period of time;
Step 5 is heated to 110 ± 1 DEG C of insulation reaction 2H, a certain amount of polyethylene glycol, polyethylene glycol and benzene sulfonic acid is added Mass ratio be 1:4~1:1,120 ± 1 DEG C of insulation reaction 2H are heated to the heating rate of 1 DEG C/min;
Step 6: steaming dichloroethanes, filters, is dried to obtain catalyst.
Further, the alcoholysis dissolved in advance that the polymeric dispersant is the volume 0.1%-0.5% of suitable water 98% polyvinyl alcohol or 1.5%-3.0% gelatin.
Further, the divinylbenzene is the dehydrogenation product of diethylbenzene, and wherein the content of divinylbenzene isomers is 65%-75%.
Further, the polymerization initiator is peroxidating dimethylamino benzoyl, and the content of the dibenzoyl peroxide is The 2.0%-3.0% of styrene, divinylbenzene and methyl acrylate and allyl itaconates monomer gross mass.
Further, in step 3, it is first warming up to 88-90 DEG C, after 88-90 DEG C of insulation reaction 2H, is warming up to 95-100 DEG C reaction 4H, be then gradually warmed up 120-125 DEG C, in 120-125 DEG C of insulation reaction 2H, then be gradually warmed up 135-150 DEG C, In 135-150 DEG C of insulation reaction 2H, finally in 150-170 DEG C of reaction 6H.
Further, the reaction condition of step 4 are as follows: feed intake under room temperature, under stiring with the heating of 10 DEG C/min after feeding intake After rate is warming up to 100 ± 1 DEG C of insulation reaction 2H, then 105 ± 1 DEG C of insulation reactions are warming up to the heating rate of 1 DEG C/10min The mass ratio of 2H, addition benzene sulfonic acid, benzene sulfonic acid and solid spherical copolymer pellet is 3:1~1:3.
Further, the distillation condition of step 6 is air-distillation, steams dichloroethanes, is then added with 2-3 DEG C/10min Heat continues air-distillation 30min to 138 DEG C or so, insulation reaction 6H, is then evaporated under reduced pressure within the scope of 138-140 DEG C to nothing Distillate stops.
Further, acid adding dilution after being cooled to 30 DEG C or less, filtering, drying.
The catalyst of the method preparation of catalyst via preparation of the invention for synthesizing polymethoxy dimethyl ether, resistance to height Temperature, 110-140 DEG C of reaction temperature can still keep higher reactivity, and the yield of reaction product is higher;Meanwhile it obtained urging Agent be solid-state, spherical shape, it is easily separated, and be catalyzed reaction after still may be reused after separation.
Specific embodiment
To be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, below in conjunction with The invention will be further described for embodiment, but not limited to this.The raw material employed in each embodiment and comparative example, except another It is commercially available product, related equipment is conventional equipment outside being described.
The present invention relates to a kind of catalyst and preparation method thereof for synthesizing polymethoxy dimethyl ether, which is used for Dimethoxym ethane and paraformaldehyde are catalyzed to prepare polymethoxy dimethyl ether.The preparation method of the solid catalyst the following steps are included:
A method of preparing the catalyst for synthesizing polymethoxy dimethyl ether comprising following steps:
Water and a certain amount of polymerization dispersion is added in the reactor equipped with speed-adjustable stir device, reflux condenser in step 1 Agent obtains aqueous phase solution;
Step 2 is added certain in styrene, divinylbenzene and methyl acrylate and allyl itaconates monomer solution The polymerization initiator and aluminium oxide of amount obtain oily phase;
The oil-phase solution is added in the aqueous phase solution by step 3, stirs to get suspension polymerisation solution, and gradually Heating, heat preservation obtain solid spherical copolymer pellet;
The solid spherical copolymer pellet, dichloroethanes and the concentrated sulfuric acid are carried out heating reaction, solid spherical by step 4 Copolymer pellet: dichloroethanes: the concentrated sulfuric acid be the proportion of three kinds of components be by weight be 0.1~0.3:0.01~0.03: 0.05~2, a certain amount of benzene sulfonic acid is added in reaction after a certain period of time;
Step 5 is heated to 110 ± 1 DEG C of insulation reaction 2H, a certain amount of polyethylene glycol, polyethylene glycol and benzene sulfonic acid is added Mass ratio be 1:4~1:1,120 ± 1 DEG C of insulation reaction 2H are heated to the heating rate of 1 DEG C/min;
Step 6: steaming dichloroethanes, filters, is dried to obtain solid, spherical catalyst.
Embodiment 1
Step 1: aqueous phase solution is prepared.In the enamel reactor of the 20000L equipped with speed-adjustable stir device, reflux condenser It is interior, the water of 1/2 volume and 0.1% 98% polyvinyl alcohol of alcoholysis dissolved in advance is added.
Step 2: oil-phase solution is prepared.By the abundant styrene dissolved with dibenzoyl peroxide and aluminium oxide, two in advance Ethenylbenzene and methyl acrylate and allyl itaconates monomer are mixed to get oil-phase solution.Divinylbenzene is that the dehydrogenation of diethylbenzene produces Object, wherein the content of divinylbenzene isomers is 65%-75%.The dosage of dibenzoyl peroxide is styrene, divinylbenzene With methyl acrylate and the 2.0% of allyl itaconates monomer gross mass.
Step 3: oil prepared by a certain amount of step step 2 is added to the water phase of a certain amount of step step 1 preparation In obtain suspension polymerization system, the proportion of monomer and water phase is 1:1.5.Stirring, monomer mixture are dispersed in water in the form of oil droplet Xiang Zhong under the stirring condition of 800 turns/min, and is gradually warmed up 88-90 DEG C;After 88-90 DEG C of insulation reaction 2H, it is warming up to 95-100 DEG C of reaction 4H, is then gradually warmed up 120-125 DEG C, in 120-125 DEG C of insulation reaction 2H, then is gradually warmed up 135- 150 DEG C, in 135-150 DEG C of insulation reaction 2H, finally in 150-170 DEG C of reaction 6H, obtain solid spherical copolymer pellet.
Step 4: in the enamel reactor equipped with blender, reflux condenser, successively plus a certain amount of solid spherical is copolymerized Composition granule, swelling agent and the concentrated sulfuric acid, in present embodiment, swelling agent is dichloroethanes, solid spherical copolymer pellet: two chloroethenes Alkane: the concentrated sulfuric acid be the proportion of three kinds of components be by weight be 0.1:0.01:0.05.Reaction condition is to feed intake under room temperature, is fed intake After being warming up to 100 ± 1 DEG C of insulation reaction 2H under stiring afterwards with the heating rate of 10 DEG C/min, then with the heating of 1 DEG C/10min Rate is warming up to 105 ± 1 DEG C of insulation reaction 2H, and 50 kilograms of benzene sulfonic acids, the matter of benzene sulfonic acid and solid spherical copolymer pellet is added Amount is than being 3:1.
Step 5: 110 ± 1 DEG C of insulation reaction 2H are heated to the heating rate of 1 DEG C/min, 25 kilograms of poly- second two are added Alcohol is heated to 120 ± 1 DEG C of insulation reaction 2H with the heating rate of 1 DEG C/min.
Step 6: air-distillation steams dichloroethanes, is then heated to 138 DEG C or so with 2-3 DEG C/10min, heat preservation is anti- Answer 6H, continue air-distillation 30min, be then evaporated under reduced pressure within the scope of 138-140 DEG C and stop to no distillate, be cooled to 30 DEG C with It after lower after acid adding dilution, filters, be dried to obtain solid, spherical catalyst.
Embodiment 2
Step 1: aqueous phase solution is prepared.In the enamel reactor equipped with speed-adjustable stir device, reflux condenser, it is added 2/3 The water of volume and 0.3% 98% polyvinyl alcohol of alcoholysis that has dissolved in advance.
Step 2: oil-phase solution is prepared.By the abundant styrene dissolved with dibenzoyl peroxide and aluminium oxide, two in advance Ethenylbenzene and methyl acrylate and allyl itaconates monomer are mixed to get oil-phase solution.Divinylbenzene is that the dehydrogenation of diethylbenzene produces Object, wherein the content of divinylbenzene isomers is 65%-75%.The dosage of dibenzoyl peroxide is styrene, divinylbenzene With methyl acrylate and the 2.5% of allyl itaconates monomer gross mass.
Step 3: oil prepared by a certain amount of step step 2 is added to the water phase of a certain amount of step step 1 preparation In obtain suspension polymerization system, the volume ratio of oil-phase solution and aqueous phase solution is 1:1.Stirring, monomer mixture is in the form of oil droplet It is dispersed in water phase, under the stirring condition of 1000 turns/min, and is gradually warmed up 88-90 DEG C;In 88-90 DEG C of insulation reaction 2H Afterwards, it is warming up to 95-100 DEG C of reaction 4H, is then gradually warmed up 120-125 DEG C, in 120-125 DEG C of insulation reaction 2H, then gradually It is warming up to 135-150 DEG C, in 135-150 DEG C of insulation reaction 2H, finally in 150-170 DEG C of reaction 6H, obtains solid spherical copolymerization Composition granule.
Step 4: in the enamel reactor equipped with blender, reflux condenser, successively plus a certain amount of solid spherical is copolymerized Composition granule, swelling agent and the concentrated sulfuric acid, in present embodiment, swelling agent is dichloroethanes, solid spherical copolymer pellet: two chloroethenes Alkane: the concentrated sulfuric acid be the proportion of three kinds of components be by weight be 0.2:0.02:1.Reaction condition be room temperature under feed intake, after feeding intake After being warming up to 100 ± 1 DEG C of insulation reaction 2H under stirring with the heating rate of 10 DEG C/min, then with the heating rate of 1 DEG C/10min It is warming up to 105 ± 1 DEG C of insulation reaction 2H, is added benzene sulfonic acid, the mass ratio of benzene sulfonic acid and solid spherical copolymer pellet is 1:1.
Step 5: (110 ± 1) DEG C insulation reaction 2H is heated to the heating rate of 1 DEG C/min, a certain amount of poly- second is added The mass ratio of glycol, polyethylene glycol and benzene sulfonic acid is 1:2, is heated to 120 ± 1 DEG C of insulation reactions with the heating rate of 1 DEG C/min 2H。
Step 6: air-distillation steams dichloroethanes, is then heated to 138 DEG C or so with 2-3 DEG C/10min, heat preservation is anti- Answer 6H, continue air-distillation 30min, be then evaporated under reduced pressure within the scope of 138-140 DEG C and stop to no distillate, be cooled to 30 DEG C with It after lower after acid adding dilution, filters, be dried to obtain solid, spherical catalyst.
Embodiment 3
Step 1: aqueous phase solution is prepared.In the enamel reactor equipped with speed-adjustable stir device, reflux condenser, it is added 2/3 The water of volume and 0.5% 98% polyvinyl alcohol of alcoholysis that has dissolved in advance.
Step 2: oil-phase solution is prepared.By the abundant styrene dissolved with dibenzoyl peroxide and aluminium oxide, two in advance Ethenylbenzene and methyl acrylate and allyl itaconates monomer are mixed to get oil-phase solution.Divinylbenzene is that the dehydrogenation of diethylbenzene produces Object, wherein the content of divinylbenzene isomers is 65%-75%.The dosage of dibenzoyl peroxide is styrene, divinylbenzene With methyl acrylate and the 3.0% of allyl itaconates monomer gross mass.
Step 3: oil prepared by a certain amount of step step 2 is added to the water phase of a certain amount of step step 1 preparation In obtain suspension polymerization system, the volume ratio of oil-phase solution and aqueous phase solution is 1:2.Stirring, monomer mixture is in the form of oil droplet It is dispersed in water phase, under the stirring condition of 1000 turns/min, and is gradually warmed up 88-90 DEG C;In 88-90 DEG C of insulation reaction 2H Afterwards, it is warming up to 95-100 DEG C of reaction 4H, is then gradually warmed up 120-125 DEG C, in 120-125 DEG C of insulation reaction 2H, then gradually It is warming up to 135-150 DEG C, in 135-150 DEG C of insulation reaction 2H, finally in 150-170 DEG C of reaction 6H, obtains solid spherical copolymerization Composition granule.
Step 4: in the enamel reactor equipped with blender, reflux condenser, successively plus a certain amount of solid spherical is copolymerized Composition granule, swelling agent and the concentrated sulfuric acid, are reacted at a certain temperature.In present embodiment, swelling agent is dichloroethanes, solid-state Spherical copolymer particle: dichloroethanes: the concentrated sulfuric acid be the proportion of three kinds of components be by weight be 0.3:0.03:2.Reaction condition To feed intake under room temperature, after being warming up to 100 ± 1 DEG C of insulation reaction 2H under stiring after feeding intake with the heating rate of 10 DEG C/min, then 105 ± 1 DEG C of insulation reaction 2H are warming up to the heating rate of 1 DEG C/10min, benzene sulfonic acid is added, benzene sulfonic acid and solid spherical are copolymerized The mass ratio of composition granule is 1:3.
Step 5: (110 ± 1) DEG C insulation reaction 2H is heated to the heating rate of 1 DEG C/min, a certain amount of poly- second is added The mass ratio of glycol, polyethylene glycol and benzene sulfonic acid is 1:1, is heated to 120 ± 1 DEG C of insulation reactions with the heating rate of 1 DEG C/min 2H。
Step 6: air-distillation steams dichloroethanes, is then heated to 138 DEG C or so with 2-3 DEG C/10min, heat preservation is anti- Answer 6H, continue air-distillation 30min, be then evaporated under reduced pressure within the scope of 138-140 DEG C and stop to no distillate, be cooled to 30 DEG C with It after lower after acid adding dilution, filters, be dried to obtain solid, spherical catalyst.
Embodiment 4
Step 1: aqueous phase solution is prepared.In the enamel reactor equipped with speed-adjustable stir device, reflux condenser, it is added 1/2 The water of volume and 1.5% gelatin.
Step 2: oil-phase solution is prepared.By the abundant styrene dissolved with dibenzoyl peroxide and aluminium oxide, two in advance Ethenylbenzene and methyl acrylate and allyl itaconates monomer are mixed to get oil-phase solution.Styrene, divinylbenzene and acrylic acid The ratio of methyl esters and allyl itaconates monomer is 3:1:0.056:0.019, and divinylbenzene is the dehydrogenation product of diethylbenzene, wherein The content of divinylbenzene isomers is 65%-75%.The dosage of dibenzoyl peroxide is styrene, divinylbenzene and acrylic acid The 2.0% of methyl esters and allyl itaconates monomer gross mass.
Step 3: oil prepared by a certain amount of step step 2 is added to the water phase of a certain amount of step step 1 preparation In obtain suspension polymerization system, the volume ratio of oil-phase solution and aqueous phase solution is 1:3.Stirring, monomer mixture is in the form of oil droplet It is dispersed in water phase, under the stirring condition of 1000 turns/min, and is gradually warmed up 88-90 DEG C;In 88-90 DEG C of insulation reaction 2H Afterwards, it is warming up to 95-100 DEG C of reaction 4H, is then gradually warmed up 120-125 DEG C, in 120-125 DEG C of insulation reaction 2H, then gradually It is warming up to 135-150 DEG C, in 135-150 DEG C of insulation reaction 2H, finally in 150-170 DEG C of reaction 6H, obtains solid spherical copolymerization Composition granule.
Step 4: in the enamel reactor equipped with blender, reflux condenser, successively plus a certain amount of solid spherical is copolymerized Composition granule, swelling agent and the concentrated sulfuric acid, are reacted at a certain temperature.In present embodiment, swelling agent is dichloroethanes, solid-state Spherical copolymer particle: dichloroethanes: the concentrated sulfuric acid be the proportion of three kinds of components be by weight be 0.3:0.03:2.Reaction condition To feed intake under room temperature, after being warming up to 100 ± 1 DEG C of insulation reaction 2H under stiring after feeding intake with the heating rate of 10 DEG C/min, then 105 ± 1 DEG C of insulation reaction 2H are warming up to the heating rate of 1 DEG C/10min, benzene sulfonic acid is added, benzene sulfonic acid and solid spherical are copolymerized The mass ratio of composition granule is 3:1~1:3.
Step 5: (110 ± 1) DEG C insulation reaction 2H is heated to the heating rate of 1 DEG C/min, a certain amount of poly- second is added The mass ratio of glycol, polyethylene glycol and benzene sulfonic acid is 1:2, is heated to 120 ± 1 DEG C of insulation reactions with the heating rate of 1 DEG C/min 2H。
Step 6: air-distillation steams dichloroethanes, is then heated to 138 DEG C or so with 2-3 DEG C/10min, heat preservation is anti- Answer 6H, continue air-distillation 30min, be then evaporated under reduced pressure within the scope of 138-140 DEG C and stop to no distillate, be cooled to 30 DEG C with It after lower after acid adding dilution, filters, be dried to obtain solid, spherical catalyst.
Embodiment 5
Step 1: aqueous phase solution is prepared.In the enamel reactor equipped with speed-adjustable stir device, reflux condenser, it is added 1/2 The water of volume and 3.0% gelatin.
Step 2: oil-phase solution is prepared.By the abundant styrene dissolved with dibenzoyl peroxide and aluminium oxide, two in advance Ethenylbenzene and methyl acrylate and allyl itaconates monomer are mixed to get oil-phase solution.Divinylbenzene is that the dehydrogenation of diethylbenzene produces Object, wherein the content of divinylbenzene isomers is 65%-75%.The dosage of dibenzoyl peroxide is styrene, divinylbenzene With methyl acrylate and the 3.0% of allyl itaconates monomer gross mass.Styrene and divinylbenzene and methyl acrylate and clothing The proportion of health allyl propionate is 3:1:0.056:0.019.
Step 3: oil prepared by a certain amount of step step 2 is added to the water phase of a certain amount of step step 1 preparation In obtain suspension polymerization system.The volume ratio of oil-phase solution liquid compatible with water is 1:1.5, and stirring, monomer mixture is with oil droplet shape Formula is dispersed in water phase, suitably adjusts speed of agitator depending on bead granule size, and be gradually warmed up 88-90 DEG C;It is protected at 88-90 DEG C After temperature reaction 2H, it is warming up to 95-100 DEG C of reaction 4H, 120-125 DEG C is then gradually warmed up, in 120-125 DEG C of insulation reaction 2H, then it is gradually warmed up 135-150 DEG C, in 135-150 DEG C of insulation reaction 2H, finally in 150-170 DEG C of reaction 6H, obtain solid-state Spherical copolymer particle.
Step 4: in the enamel reactor equipped with blender, reflux condenser, successively plus a certain amount of solid spherical is copolymerized Composition granule, swelling agent and the concentrated sulfuric acid, in present embodiment, swelling agent is dichloroethanes, solid spherical copolymer pellet: two chloroethenes Alkane: the concentrated sulfuric acid be the proportion of three kinds of components be by weight be 0.2:0.02:1.Reaction condition be room temperature under feed intake, after feeding intake After being warming up to 100 ± 1 DEG C of insulation reaction 2H under stirring with the heating rate of 10 DEG C/min, then with the heating rate of 1 DEG C/10min It is warming up to 105 ± 1 DEG C of insulation reaction 2H, is added benzene sulfonic acid, the mass ratio of benzene sulfonic acid and solid spherical copolymer pellet is 1:3.
Step 5: (110 ± 1) DEG C insulation reaction 2H is heated to the heating rate of 1 DEG C/min, a certain amount of poly- second is added The mass ratio of glycol, polyethylene glycol and benzene sulfonic acid is 1:2, is heated to 120 ± 1 DEG C of insulation reactions with the heating rate of 1 DEG C/min 2H。
Step 6: air-distillation steams dichloroethanes, is then heated to 138 DEG C or so with 2-3 DEG C/10min, heat preservation is anti- Answer 6H, continue air-distillation 30min, be then evaporated under reduced pressure within the scope of 138-140 DEG C and stop to no distillate, be cooled to 30 DEG C with It after lower after acid adding dilution, filters, be dried to obtain this solid, spherical catalyst.
Catalyst prepared by the above method is used to be catalyzed dimethoxym ethane and paraformaldehyde to prepare polymethoxy dimethyl ether, is had Body embodiment please refers to embodiment 6-10.
Embodiment 6
3g catalyst prepared by the present invention, 100g dimethoxym ethane and 100g trimerization first are added in 300 milliliters of tank reactors Aldehyde reacts 4h at 110 DEG C, 2.8g catalyst and reaction mixture 180g is obtained by filtration, reaction mixture is by gas-chromatography point Result is analysed see table one.
Embodiment 7
Catalyst prepared by the 2g embodiment of the present invention 1,100g dimethoxym ethane and 100g are added in 300 milliliters of tank reactors Metaformaldehyde reacts 4h at 120 DEG C, 1.7g catalyst and reaction mixture 175g is obtained by filtration, reaction mixture is by gas phase Chromatography result is see table one.
Embodiment 8
In 300 milliliters of tank reactors be added the 2.5g embodiment of the present invention 1 prepare catalyst, 100g dimethoxym ethane and 100g metaformaldehyde reacts 4h at 130 DEG C, is obtained by filtration 2.2g catalyst and reaction mixture 178g, reaction mixture by Gas chromatographic analysis result is see table one.
Embodiment 9
Catalyst prepared by the 2g embodiment of the present invention 1,100g dimethoxym ethane and 100g are added in 300 milliliters of tank reactors Metaformaldehyde reacts 4h at 140 DEG C, 1.6g catalyst and reaction mixture 182g is obtained by filtration, reaction mixture is by gas phase Chromatography result is see table one.
Embodiment 10
In 300 milliliters of tank reactors be added the filtered catalyst of the 2g embodiment of the present invention 6,100g dimethoxym ethane and 100g metaformaldehyde reacts 4h at 140 DEG C, is obtained by filtration 1.8g catalyst and reaction mixture 172g, reaction mixture by Gas chromatographic analysis result is see table one.
Table one: catalysis reaction result analytical table
Sample DMM2 DMM3 DMM4 DMM5-10 DMM2-10 Other
Embodiment 6 21.3 20.0 16.4 21.4 79.1 Surplus
Embodiment 7 18.2 14.6 16.1 18.6 67.5 Surplus
Embodiment 8 19.5 17.8 19.2 20.9 77.4 Surplus
Embodiment 9 18.7 17.4 19.9 20.0 76.0 Surplus
Embodiment 10 19.0 16.5 17.3 19.3 72.1 Surplus
Remarks: the content of each component DMM2, DMM3, DMM4, DMM5-10, DMM2-10 are mass percentage in table one.
From embodiment 6-10 and table one, it can be concluded that, catalyst high temperature resistant of the invention, 110-140 DEG C of reaction temperature still may be used To keep higher reactivity, be conducive to the abundant progress of reaction, the yield of reaction product is higher;Meanwhile this catalyst by Then solid-state may be reused after separation after reaction, reduce costs, avoid pollution environment;N=2- in reaction product 4 50% or more product assay, the product dissolubility of n=2-4 is good, and DMM2-10 increases tune as cleaning diesel oil blending component With the mobility of rear cleaning diesel oil, viscosity is reduced.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention Within the scope of shield.

Claims (6)

1. a kind of method for preparing the catalyst for synthesizing polymethoxy dimethyl ether comprising following steps:
Step 1 is added water and a certain amount of polymeric dispersant obtains in the reactor equipped with speed-adjustable stir device, reflux condenser To aqueous phase solution;
Step 2 is added a certain amount of in styrene, divinylbenzene and methyl acrylate and allyl itaconates monomer solution Polymerization initiator and aluminium oxide obtain oily phase;
The oil-phase solution is added in the aqueous phase solution by step 3, stirs to get suspension polymerisation solution, and gradually rise Temperature, heat preservation obtain solid spherical copolymer pellet;In step 3, it is first warming up to 88-90 DEG C, after 88-90 DEG C of insulation reaction 2H, It is warming up to 95-100 DEG C of reaction 4H, is then gradually warmed up 120-125 DEG C, in 120-125 DEG C of insulation reaction 2H, then is gradually warmed up To 135-150 DEG C, in 135-150 DEG C of insulation reaction 2H, finally in 150-170 DEG C of reaction 6H;
The solid spherical copolymer pellet, dichloroethanes and the concentrated sulfuric acid are carried out heating reaction, solid spherical copolymerization by step 4 Composition granule: dichloroethanes: the concentrated sulfuric acid be the proportion of three kinds of components be by weight 0.1~0.3:0.01~0.03:0.05~ 2, a certain amount of benzene sulfonic acid is added in reaction after a certain period of time;The reaction condition of step 4 are as follows: feed intake under room temperature, stirred after feeding intake Under 100 ± 1 DEG C of insulation reaction 2H are warming up to the heating rate of 10 DEG C/min after, then heated up with the heating rate of 1 DEG C/10min To 105 ± 1 DEG C of insulation reaction 2H, it is added benzene sulfonic acid, the mass ratio of benzene sulfonic acid and solid spherical copolymer pellet is 3:1~1:3;
Step 5 is heated to 110 ± 1 DEG C of insulation reaction 2H, and a certain amount of polyethylene glycol, the matter of polyethylene glycol and benzene sulfonic acid is added Amount is heated to 120 ± 1 DEG C of insulation reaction 2H than being 1:4~1:1 with the heating rate of 1 DEG C/min;
Step 6: steaming dichloroethanes, filters, is dried to obtain catalyst.
2. method of the preparation as described in claim 1 for synthesizing the catalyst of polymethoxy dimethyl ether, it is characterised in that: institute State 98% polyvinyl alcohol of alcoholysis or 1.5%- of the volume 0.1%-0.5% that polymeric dispersant is suitable water dissolved in advance 3.0% gelatin.
3. method of the preparation as described in claim 1 for synthesizing the catalyst of polymethoxy dimethyl ether, it is characterised in that: institute The dehydrogenation product that divinylbenzene is diethylbenzene is stated, wherein the content of divinylbenzene isomers is 65%-75%.
4. method of the preparation as described in claim 1 for synthesizing the catalyst of polymethoxy dimethyl ether, it is characterised in that: institute Stating polymerization initiator is dibenzoyl peroxide, and the content of the dibenzoyl peroxide is styrene, divinylbenzene and propylene The 2.0%-3.0% of sour methyl esters and allyl itaconates monomer gross mass.
5. method of the preparation as described in claim 1 for synthesizing the catalyst of polymethoxy dimethyl ether, it is characterised in that: step Rapid six distillation condition is air-distillation, steams dichloroethanes, is then heated to 138 DEG C or so with 2-3 DEG C/10min, heat preservation is anti- 6H is answered, air-distillation 30min is continued, then vacuum distillation to no distillate stops within the scope of 138-140 DEG C.
6. method of the preparation as claimed in claim 5 for synthesizing the catalyst of polymethoxy dimethyl ether, it is characterised in that: drop Temperature filters to acid adding dilution after 30 DEG C or less, is dry.
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