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 PDFInfo
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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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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- 238000009413 insulation Methods 0.000 claims abstract description 52
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 239000012071 phase Substances 0.000 claims abstract description 34
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 25
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940092714 benzenesulfonic acid Drugs 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 allyl itaconates Chemical class 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 239000008188 pellet Substances 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008346 aqueous phase Substances 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 36
- 238000010792 warming Methods 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical group CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 13
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 13
- 239000008187 granular material Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 235000021050 feed intake Nutrition 0.000 claims description 7
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 13
- 210000003298 dental enamel Anatomy 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 230000008961 swelling Effects 0.000 description 10
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
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
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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| CN103848729A (en) * | 2012-12-07 | 2014-06-11 | 华东理工大学 | Method for preparing polyoxymethylenedimethylether by using methanol and formaldehyde |
| CN105585461A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Synthesis method of polyoxymethylene dimethyl ether |
| CN105583008A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Polyoxymethylene dimethyl ether catalyst and preparation method thereof |
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| CN102585076A (en) * | 2011-12-27 | 2012-07-18 | 深圳清华大学研究院 | Macroporous resin microspheres and preparation method and application thereof |
| CN103848729A (en) * | 2012-12-07 | 2014-06-11 | 华东理工大学 | Method for preparing polyoxymethylenedimethylether by using methanol and formaldehyde |
| CN105585461A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Synthesis method of polyoxymethylene dimethyl ether |
| CN105583008A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Polyoxymethylene dimethyl ether catalyst and preparation method thereof |
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