CN112239396A - Preparation method and application of polyformaldehyde dimethyl ether - Google Patents
Preparation method and application of polyformaldehyde dimethyl ether Download PDFInfo
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- CN112239396A CN112239396A CN201910643845.5A CN201910643845A CN112239396A CN 112239396 A CN112239396 A CN 112239396A CN 201910643845 A CN201910643845 A CN 201910643845A CN 112239396 A CN112239396 A CN 112239396A
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- -1 polyoxymethylene dimethyl ether Polymers 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 19
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000005086 pumping Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 239000002283 diesel fuel Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000008098 formaldehyde solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 3
- 239000002816 fuel additive Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000005218 dimethyl ethers Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/30—Chemical modification by after-treatment
- C08G2/34—Chemical modification by after-treatment by etherification
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Combustion & Propulsion (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a preparation method and application of polyoxymethylene dimethyl ether, which comprises the following steps: pumping methanol, methylal and formaldehyde aqueous solution into a microchannel reactor filled with the treated cation exchange resin particle catalyst for reaction; and introducing the mixed solution after the reaction of the microchannel reactor into the first separation tower, the second separation tower and the third separation tower, and heating and pressurizing to obtain the polyformaldehyde dimethyl ether with low polymerization degree and the polyformaldehyde dimethyl ether with high polymerization degree. According to the preparation method and the application of the polyformaldehyde dimethyl ether, the microchannel reactor is used, so that the preparation process time is short, the reaction efficiency is high, meanwhile, the reaction temperature can be accurately controlled, and the reaction safety and stability are ensured; through the action of the first separation tower, the second separation tower and the third separation tower, the obtained polyformaldehyde dimethyl ether with low polymerization degree and the polyformaldehyde dimethyl ether with high polymerization degree are separated, and the purity and the using effect of the product are improved.
Description
Technical Field
The invention relates to a preparation method and application of polyoxymethylene dimethyl ether, belonging to the technical field of polymer synthesis and application.
Background
Diesel engines have received increased attention because of their higher compression ratio and higher thermal efficiency than gasoline engines. The pollutants emitted by diesel engines mainly include solid particulates, nitrogen oxides, hydrocarbons and carbon oxides. PM2.5 in the solid particulate matter contains a large amount of carcinogenic substances and can cause pathological changes of a respiratory system. With the increasing requirements of people on living environment, the country strictly controls the emission of pollutants, so the emission of the diesel engine must meet the national standard. The specific additives are added into the diesel oil, so that the quality of the diesel oil can be improved, and the emission pollution condition of the diesel oil can be reduced.
The fuel additives can be roughly classified into three categories according to their functions, namely, combustion-promoting type, oil quality-improving type and smoke-eliminating and pollution-reducing type. The types of smoke abatement and pollution reduction fuel additives are very many, and the common fuel additive is polyoxymethylene dimethyl ether (PODE for short)n) Polymethoxy dimethyl ether with molecular formula of CH3O(CH2O)nCH3With n being different, PODEnThe physical properties such as boiling point and cetane number and application properties of the composition are also changed. The fuel additive is not only low in price and suitable for large-scale use on diesel oil, but also has no high pollution to the environment.
The raw materials for synthesizing the polyoxymethylene dimethyl ethers comprise compounds capable of providing paraformaldehyde in the middle section (such as formaldehyde, trioxymethylene and paraformaldehyde) and compounds capable of providing methyl groups with two end groups (such as methanol, dimethyl ether and methylal).
The patent publication No. CN109134210A discloses the production of polyoxymethylene dimethyl ethers by using molecular catalysts. Specifically, trioxymethylene (1, 3, 5-trioxane) and methylal (CH)2(OCH3)2) Under the condition of existence of a synthetic catalyst and a molecular sieve supported catalyst, performing oxidation catalytic reaction to prepare polyoxymethylene dimethyl ether; wherein the volume ratio of raw materials of trioxymethylene and methylal is 2: 9, wherein the oxidation catalytic synthesis reaction is carried out for about 6 hours at the temperature of 80-120 ℃, and the contents or volume fractions of the synthetic catalyst and the molecular sieve supported catalyst in the oxidation catalytic reaction system in the oxidation catalytic synthesis reaction process are respectively 2% and 10%. The product is obtained by the existence of the synthesis catalyst and the molecular sieve supported catalyst, although the reaction yield is improved, the reaction yield is improvedThe pore size of the molecular sieve supported catalyst is not easy to control, the production period is long, and the obtained product is a mixture of polyformaldehyde dimethyl ethers with different polymerization degrees, so that the method has influence on the application of the method to industrial production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method and application of polyoxymethylene dimethyl ether.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of polyoxymethylene dimethyl ether comprises the following steps:
(1) pumping methanol, methylal and formaldehyde aqueous solution into a microchannel reactor filled with the treated cation exchange resin particle catalyst for reaction;
(2) introducing the mixed solution after the reaction of the microchannel reactor into a first separation tower, heating and pressurizing, and carrying out rectification separation to obtain a tower top material A and a tower bottom material B;
(3) introducing the tower top material A into a second separation tower, heating and pressurizing to obtain a tower top material C and a tower bottom material D, wherein the tower top material C is a methanol aqueous solution, and the tower bottom material D is polyformaldehyde dimethyl ether with low polymerization degree;
(4) and (3) introducing the tower bottom material B into a third separation tower, heating and pressurizing to obtain a tower top material E and a tower bottom material F, wherein the tower top material E is polyformaldehyde dimethyl ether with low polymerization degree, and the tower bottom material F is polyformaldehyde dimethyl ether with high polymerization degree.
Preferably, the mass ratio of the methanol to the methylal to the formaldehyde aqueous solution is 5-10: 3-5: 20-50.
Preferably, the concentration of the aqueous formaldehyde solution is 25 wt% to 35 wt%.
Preferably, the pumping flow rate in the step (1) is 0.1L/h-2.0L/h
Preferably, the reaction temperature in the microchannel reactor is 100-150 ℃, and the reaction pressure is 0.3-1.5 MPa.
Preferably, the treatment method of the cation exchange resin particle catalyst is as follows:
(1) stirring and soaking cation exchange resin particles in absolute ethyl alcohol for 3-6 hours, wherein the volume ratio of the resin to the absolute ethyl alcohol is 1: 4-8;
(2) washing the resin soaked in the ethanol with deionized water, and then drying the resin;
(3) soaking the dried resin for 3-6 h by using a hydrochloric acid solution with the concentration of 1mol/L, wherein the volume ratio of the resin to the hydrochloric acid solution is 1: 6-10;
(4) washing the resin soaked in the acid again by using deionized water until the pH value of the water is 6-7;
(5) washing away water in the wet resin catalyst by using absolute ethyl alcohol;
(6) and (4) drying the resin.
Preferably, the temperature in the first separation tower is 130-160 ℃, and the pressure is 50-70 kPa.
Preferably, the temperature in the second separation tower is 80-110 ℃, and the pressure is 80-100 kPa.
Preferably, the temperature in the third separation tower is 150-180 ℃, and the pressure is 60-80 kPa.
The invention also provides application of the polyformaldehyde dimethyl ether prepared by the preparation method of the polyformaldehyde dimethyl ether in diesel oil.
In conclusion, the invention has the following beneficial effects:
(1) according to the preparation method and the application of the polyformaldehyde dimethyl ether, the microchannel reactor is used, so that the preparation process time is short, the reaction efficiency is high, and meanwhile, the reaction in the microchannel reactor can be realized, so that the method is simple and rapid, the reaction temperature can be accurately controlled, and the reaction safety and stability are ensured; the obtained polyformaldehyde dimethyl ether with low polymerization degree and polyformaldehyde dimethyl ether with high polymerization degree are separated through the action of the first separation tower, the second separation tower and the third separation tower, so that the purity and the using effect of the product are improved;
(2) according to the preparation method and application of the polyformaldehyde dimethyl ether, the treated cation exchange resin particle catalyst is adopted, so that the catalyst is low in treatment cost and good in reaction activity, and the reaction speed is increased;
(3) according to the preparation method and the application of the polyformaldehyde dimethyl ether, the polyformaldehyde dimethyl ether with high polymerization degree obtained by separation can be applied to diesel oil, so that the performance of the diesel oil is improved.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
A preparation method of polyoxymethylene dimethyl ether comprises the following steps:
(1) pumping 50g of methanol, 30g of methylal and 200g of 25 wt% aqueous formaldehyde solution into a microchannel reactor filled with 2.6g of treated cation exchange resin particle catalyst at a flow rate of 0.1L/h for reaction, wherein the reaction temperature is 100 ℃ and the reaction pressure is 0.3 MPa;
(2) introducing the mixed solution after the reaction of the microchannel reactor into a first separation tower, heating and pressurizing at the temperature of 130 ℃ and under the pressure of 50kPa, and carrying out rectification separation to obtain a tower top material A and a tower bottom material B;
(3) introducing the tower top material A into a second separation tower, heating and pressurizing at 80 ℃, and separating to obtain a tower top material C and a tower bottom material D, wherein the tower top material C is a methanol aqueous solution, and the tower bottom material D is polyformaldehyde dimethyl ether with low polymerization degree;
(4) and (3) introducing the tower bottom material B into a third separation tower, heating and pressurizing at the temperature of 150 ℃ and under the pressure of 60kPa to obtain a tower top material E and a tower bottom material F, wherein the tower top material E is polyformaldehyde dimethyl ether with low polymerization degree, and the tower bottom material F is polyformaldehyde dimethyl ether with high polymerization degree.
The treatment method of the cation exchange resin particle catalyst comprises the following steps:
(1) stirring and soaking a cation exchange resin particle catalyst in absolute ethyl alcohol for 3 hours, wherein the volume ratio of the resin to the absolute ethyl alcohol is 1: 4;
(2) washing the resin soaked in the ethanol with deionized water, and then drying the resin;
(3) soaking the dried resin for 3 hours by using a hydrochloric acid solution with the concentration of 1mol/L, wherein the volume ratio of the resin to the hydrochloric acid solution is 1: 6;
(4) washing the resin soaked by the acid again by using deionized water until the pH value of the water is 7;
(5) washing away water in the wet resin catalyst by using absolute ethyl alcohol;
(6) and (4) drying the resin.
An application of polyoxymethylene dimethyl ether prepared by the preparation method of polyoxymethylene dimethyl ether in diesel oil.
Example 2
A preparation method of polyoxymethylene dimethyl ether comprises the following steps:
(1) pumping 100g of methanol, 50g of methylal and 500g of 35 wt% aqueous formaldehyde solution into a microchannel reactor filled with 16g of treated cation exchange resin particle catalyst at a flow rate of 2.0L/h for reaction, wherein the reaction temperature is 150 ℃ and the reaction pressure is 1.5 MPa;
(2) introducing the mixed solution after the reaction of the microchannel reactor into a first separation tower, heating and pressurizing at 160 ℃ and 70kPa, and carrying out rectification separation to obtain a tower top material A and a tower bottom material B;
(3) introducing the tower top material A into a second separation tower, heating and pressurizing at the temperature of 110 ℃ and under the pressure of 100kPa, and separating to obtain a tower top material C and a tower bottom material D, wherein the tower top material C is a methanol aqueous solution, and the tower bottom material D is polyformaldehyde dimethyl ether with low polymerization degree;
(4) and (3) introducing the tower bottom material B into a third separation tower, heating and pressurizing at 180 ℃ and under 80kPa to obtain a tower top material E and a tower bottom material F, wherein the tower top material E is polyformaldehyde dimethyl ether with low polymerization degree, and the tower bottom material F is polyformaldehyde dimethyl ether with high polymerization degree.
The treatment method of the cation exchange resin particle catalyst comprises the following steps:
(1) stirring and soaking a cation exchange resin particle catalyst in absolute ethyl alcohol for 6 hours, wherein the volume ratio of the resin to the absolute ethyl alcohol is 1: 8;
(2) washing the resin soaked in the ethanol with deionized water, and then drying the resin;
(3) soaking the dried resin for 6 hours by using a hydrochloric acid solution with the concentration of 1mol/L, wherein the volume ratio of the resin to the hydrochloric acid solution is 1: 10;
(4) washing the resin soaked by the acid again by using deionized water until the pH value of the water is 6;
(5) washing away water in the wet resin catalyst by using absolute ethyl alcohol;
(6) and (4) drying the resin.
An application of polyoxymethylene dimethyl ether prepared by the preparation method of polyoxymethylene dimethyl ether in diesel oil.
Example 3
A preparation method of polyoxymethylene dimethyl ether comprises the following steps:
(1) pumping 80g of methanol, 40g of methylal and 400g of 30 wt% aqueous formaldehyde solution into a microchannel reactor filled with 7.8g of treated cation exchange resin particle catalyst at a flow rate of 1.0L/h for reaction, wherein the reaction temperature is 130 ℃ and the reaction pressure is 0.9 MPa;
(2) introducing the mixed solution after the reaction of the microchannel reactor into a first separation tower, heating and pressurizing at 1450 ℃ and 60kPa, and carrying out rectification separation to obtain a tower top material A and a tower bottom material B;
(3) introducing the tower top material A into a second separation tower, heating and pressurizing at 100 ℃ and under the pressure of 90kPa, and separating to obtain a tower top material C and a tower bottom material D, wherein the tower top material C is a methanol aqueous solution, and the tower bottom material D is polyformaldehyde dimethyl ether with low polymerization degree;
(4) and (3) introducing the tower bottom material B into a third separation tower, heating and pressurizing at 160 ℃ under 70kPa to obtain a tower top material E and a tower bottom material F, wherein the tower top material E is polyformaldehyde dimethyl ether with low polymerization degree, and the tower bottom material F is polyformaldehyde dimethyl ether with high polymerization degree.
The treatment method of the cation exchange resin particle catalyst comprises the following steps:
(1) stirring and soaking a cation exchange resin particle catalyst in absolute ethyl alcohol for 5 hours, wherein the volume ratio of the resin to the absolute ethyl alcohol is 1: 6;
(2) washing the resin soaked in the ethanol with deionized water, and then drying the resin;
(3) soaking the dried resin for 4 hours by using a hydrochloric acid solution with the concentration of 1mol/L, wherein the volume ratio of the resin to the hydrochloric acid solution is 1: 8;
(4) washing the resin soaked by the acid again by using deionized water until the pH value of the water is 6;
(5) washing away water in the wet resin catalyst by using absolute ethyl alcohol;
(6) and (4) drying the resin.
An application of polyoxymethylene dimethyl ether prepared by the preparation method of polyoxymethylene dimethyl ether in diesel oil.
According to the preparation method and the application of the polyformaldehyde dimethyl ether, the microchannel reactor is used, so that the preparation process time is short, the reaction efficiency is high, and meanwhile, the reaction in the microchannel reactor can be realized, so that the method is simple and rapid, the reaction temperature can be accurately controlled, and the reaction safety and stability are ensured; the obtained polyformaldehyde dimethyl ether with low polymerization degree and polyformaldehyde dimethyl ether with high polymerization degree are separated through the action of the first separation tower, the second separation tower and the third separation tower, so that the purity and the using effect of the product are improved; according to the preparation method and application of the polyformaldehyde dimethyl ether, the treated cation exchange resin particle catalyst is adopted, so that the catalyst is low in treatment cost and good in reaction activity, and the reaction speed is increased; according to the preparation method and the application of the polyformaldehyde dimethyl ether, the polyformaldehyde dimethyl ether with high polymerization degree obtained by separation can be applied to diesel oil, so that the performance of the diesel oil is improved.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. The preparation method of the polyoxymethylene dimethyl ether is characterized by comprising the following steps:
(1) pumping methanol, methylal and formaldehyde aqueous solution into a microchannel reactor filled with the treated cation exchange resin particle catalyst for reaction;
(2) introducing the mixed solution after the reaction of the microchannel reactor into a first separation tower, heating and pressurizing, and carrying out rectification separation to obtain a tower top material A and a tower bottom material B;
(3) introducing the tower top material A into a second separation tower, heating and pressurizing to obtain a tower top material C and a tower bottom material D, wherein the tower top material C is a methanol aqueous solution, and the tower bottom material D is polyformaldehyde dimethyl ether with low polymerization degree;
(4) and (3) introducing the tower bottom material B into a third separation tower, heating and pressurizing to obtain a tower top material E and a tower bottom material F, wherein the tower top material E is polyformaldehyde dimethyl ether with low polymerization degree, and the tower bottom material F is polyformaldehyde dimethyl ether with high polymerization degree.
2. The preparation method of polyoxymethylene dimethyl ether according to claim 1, wherein the mass ratio of methanol to methylal to the aqueous formaldehyde solution is 5-10: 3-5: 20 to 50.
3. The method for preparing polyoxymethylene dimethyl ethers according to claim 2, wherein the concentration of the aqueous formaldehyde solution is 25 to 35 wt%.
4. The method for preparing polyoxymethylene dimethyl ethers according to claim 1, wherein the pumping rate in step (1) is 0.1L/h to 2.0L/h.
5. The preparation method of polyoxymethylene dimethyl ether according to claim 1, wherein a reaction temperature in the microchannel reactor is 100 to 150 ℃ and a reaction pressure is 0.3 to 1.5 MPa.
6. The method for preparing polyoxymethylene dimethyl ethers according to claim 1, wherein the method for treating the cation exchange resin particle catalyst comprises:
(1) stirring and soaking cation exchange resin particles in absolute ethyl alcohol for 3-6 h, wherein the volume ratio of the resin to the absolute ethyl alcohol is 1: 4-8;
(2) washing the resin soaked in the ethanol with deionized water, and then drying the resin;
(3) soaking the dried resin for 3-6 h by using a hydrochloric acid solution with the concentration of 1mol/L, wherein the volume ratio of the resin to the hydrochloric acid solution is 1: 6-10;
(4) washing the resin soaked in the acid again by using deionized water until the pH value of the water is 6-7;
(5) washing away water in the wet resin catalyst by using absolute ethyl alcohol;
(6) and (4) drying the resin.
7. The method for preparing polyoxymethylene dimethyl ethers according to claim 1, wherein the temperature in the first separation column is 130 to 160 ℃ and the pressure is 50 to 70 kPa.
8. The method for preparing polyoxymethylene dimethyl ethers according to claim 1, wherein the temperature in the second separation column is 80 to 110 ℃ and the pressure is 80 to 100 kPa.
9. The method for preparing polyoxymethylene dimethyl ethers according to claim 1, wherein the temperature in the third separation column is 150 to 180 ℃ and the pressure is 60 to 80 kPa.
10. The application of the polyoxymethylene dimethyl ethers prepared by the preparation method of polyoxymethylene dimethyl ethers according to any one of claims 1 to 9 in diesel oil.
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