CN103664546B - Prepare the method for polymethoxy dimethyl ether - Google Patents

Prepare the method for polymethoxy dimethyl ether Download PDF

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Publication number
CN103664546B
CN103664546B CN201210324500.1A CN201210324500A CN103664546B CN 103664546 B CN103664546 B CN 103664546B CN 201210324500 A CN201210324500 A CN 201210324500A CN 103664546 B CN103664546 B CN 103664546B
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dimethyl ether
catalyzer
reaction
polymethoxy dimethyl
hours
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CN103664546A (en
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何欣
刘志成
高焕新
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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

Abstract

The present invention relates to a kind of method preparing polymethoxy dimethyl ether, mainly there is catalyzer in solution prior art and there is corrosive problem.The present invention is by adopting with methyl alcohol or dme and formaldehyde or trioxymethylene as raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.1 ~ 10, it is 50 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.1 ~ 10MPa condition, and reaction raw materials and catalyst exposure generate polymethoxy dimethyl ether; ZSM-5 catalyzer wherein used is prepared as follows: by silicon source, aluminium source, alkali source, Yanyuan and water mixing, reaction mixture is with molar ratio computing SiO 2: Al 2o 3: OH -: Cl -: H 2o=1:0.0025 ~ 0.05:0.1 ~ 0.6:0.05 ~ 0.5:20 ~ 200; By said mixture 60 ~ 120 DEG C of crystallization 2 ~ 24 hours, again 140 ~ 200 DEG C of crystallization 2 ~ 72 hours, products therefrom is after separation, washing, drying, ammonium friendship, roasting, the technical scheme obtaining described catalyzer solves this problem preferably, can be used for preparing in the industrial production of polymethoxy dimethyl ether.

Description

Prepare the method for polymethoxy dimethyl ether
Technical field
The present invention relates to a kind of method preparing polymethoxy dimethyl ether.
Background technology
(Chinese also can be polyoxymethylene dimethyl ether to polymethoxy dimethyl ether, polyoxymethylene dimethyl ethers, polymethoxy methylal, polyoxymethylene dimethyl ethers, polymethoxy dimethyl ether, polyoxy methylene dimethyl ether etc.), i.e. polyoxymethylenedimethylethers (PODE), it is the common name of a class material, and its molecular structural formula is CH 3o (CH 2o) ncH 3, there is higher cetane value (cetanenumber, CN.During n=3 ~ 8, CN>76) and oxygen level (42 ~ 49%).When the value of n is 3 ~ 8, its physical and chemical performance, combustionproperty and diesel oil closely, can be used as diesel-dope, and the addition in diesel oil can reach 30% (v/v), keeps higher cetane value and combustionproperty simultaneously.The oilness of diesel oil can be improved, reduce combustion fumes and generate, diesel oil combustion position within the engine can be improved, improve thermo-efficiency, reduce the particulate matter in combustion tail gas and NO xdischarge.Also possibility diesel oil substitute, directly as diesel-fuel.
Polymethoxy dimethyl ether is solve the defect that dme does the existence of derv fuel oil blend component as the main purpose that Novel clean oil dope is researched and developed.Rich coal resources in China, has strategic importance and good economic worth by coal-based methanol combined diesel oil blend component, is day by day subject to people's attention.
US2449469 disclose a kind of with methylal and paraformaldehyde for raw material, the method using sulfuric acid as the polymethoxy dimethyl ether of catalyst preparing n=2 ~ 4, but there is the serious problem of catalytic erosion.
WO2006/045506A1 discloses BASF AG and uses sulfuric acid or trifluoromethanesulfonic acid as catalyzer, with methyl alcohol, methylal, trioxymethylene, paraformaldehyde etc. for raw material, obtains the series product of n=1 ~ 10, there is the problem that catalytic erosion is serious equally.
US5746785 disclose a kind of with 0.1wt% formic acid for catalyzer, with methylal and paraformaldehyde or methyl alcohol and paraformaldehyde for raw material, there is the problem that catalytic erosion is serious in the series product of preparation n=1 ~ 10 equally.
CN101182367A and CN101962318A discloses and adopts acidic ion liquid as catalyzer, is the method that polymethoxy dimethyl ether prepared by raw material, there is the problem that catalytic erosion is serious equally by methyl alcohol and trioxymethylene.
CN101665414A discloses a kind of acidic ion liquid that adopts as catalyzer, is the method that polymethoxy dimethyl ether prepared by raw material, there is the problem that catalytic erosion is serious equally by methylal and trioxymethylene.
In sum, the catalyzer adopted in conventional art has corrosive shortcoming.
Summary of the invention
Technical problem to be solved by this invention there is catalyzer in conventional art to have corrosive problem, provides a kind of method preparing polymethoxy dimethyl ether newly.The method has the free from corrosion advantage of catalyzer.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method preparing polymethoxy dimethyl ether, with methyl alcohol or dme and formaldehyde or trioxymethylene for raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.1 ~ 10, it is 50 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.1 ~ 10MPa condition, and reaction raw materials and ZSM-5 catalyst exposure generate polymethoxy dimethyl ether; Catalyst levels is 0.01 ~ 15% of reaction raw materials weight; ZSM-5 catalyzer wherein used is prepared as follows:
By silicon source, aluminium source, alkali source, Yanyuan and water mixing, reaction mixture is with molar ratio computing SiO 2: Al 2o 3: OH -: Cl -: H 2o=1:0.0025 ~ 0.05:0.1 ~ 0.6:0.05 ~ 0.5:20 ~ 200; By said mixture 60 ~ 120 DEG C of crystallization 2 ~ 24 hours, then 140 ~ 200 DEG C of crystallization 2 ~ 72 hours, products therefrom through being separated, washing, dry, ammonium is handed over, after roasting, obtain described catalyzer; Wherein said silicon source is selected from least one in diatomite, water glass, silicon sol or White Carbon black, aluminium source is selected from least one in sodium metaaluminate, Tai-Ace S 150 or aluminum nitrate, alkali source is selected from least one in sodium hydroxide or potassium hydroxide, and Yanyuan is selected from least one in sodium-chlor or Repone K.
In technique scheme, reaction mixture is with molar ratio computing SiO 2: Al 2o 3: OH -: Cl -: H 2o preferable range is 1:0.005 ~ 0.02:0.15 ~ 0.4:0.08 ~ 0.4:30 ~ 100.The crystal grain diameter of ZSM-5 catalyzer is preferably less than 3 microns.
Methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio preferable range are 1:0.5 ~ 6.Formaldehyde can be the formaldehyde solution of 10 ~ 80wt%, or paraformaldehyde or trioxymethylene.Catalyst levels is the preferable range of reaction raw materials weight is 0.1 ~ 10%.Temperature of reaction preferable range is 70 ~ 150 DEG C, and reaction pressure preferable range is 0.5 ~ 6MPa.
The small-grain ZSM-5 that the present invention is prepared by adopting organic-free template, owing to not introducing any organic formwork agent in building-up process, also keep unimpeded without its duct of roasting, overcome the shortcoming that can damage zeolite framework when roasting removes organic formwork agent.The present inventor finds uncannily, adopt the inventive method, under temperature 130 DEG C, pressure 6MPa react 2 hours, n be 3 ~ 8 product can reach 32.2% in products distribution; The most important thing is that catalyzer non-corrosiveness achieves good technique effect.
Accompanying drawing explanation
The XRD spectra of the ZSM-5 zeolite that Fig. 1 synthesizes for [embodiment 1].
The SEM photo of the ZSM-5 zeolite that Fig. 2 synthesizes for [embodiment 1].
In Fig. 1, X-ray diffracting spectrum has strong diffraction peak at 23.2,7.9,24,8.8,23.6 and 24.4 degree of places, and illustrating that this zeolite has MFI topological framework, is ZSM-5 zeolite.
In Fig. 2, can find out, this zeolite average crystal grain size about 1 micron.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
By SiO 2: Al 2o 3: OH -: Cl -: H 2o=1:0.017:0.2:0.1:30.Take each material, sodium aluminate is dissolved in distilled water, then drip silicon sol, stir 1 hour, then drip sodium chloride aqueous solution, stir 1 hour, then drip aqueous sodium hydroxide solution, then continue stirring 5 hours.Gained mixture crystallization 10 hours under 100 DEG C of hydrothermal conditions, then under 170 DEG C of hydrothermal conditions crystallization 24 hours, washing and filtering is also dried, then ammonium exchanges, dry, roasting, obtains catalyzer.XRD spectra is shown in Fig. 1, and Fig. 2 is shown in by SEM photo.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 2 grams of catalyzer, 100 grams of methyl alcohol, 100 grams of trioxymethylenes, 130 DEG C and made pressure be 6MPa by inflated with nitrogen under react 2 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, reaction result is in table 1.
[embodiment 2]
By SiO 2: Al 2o 3: OH -: Cl -: H 2o=1:0.01:0.25:0.2:41.Take each material, Tai-Ace S 150 is dissolved in distilled water, then drip silicon sol, stir 1 hour, then drip potassium chloride solution, stir 1 hour, then drip potassium hydroxide aqueous solution, then continue stirring 5 hours.Gained mixture crystallization 12 hours under 90 DEG C of hydrothermal conditions, then under 180 DEG C of hydrothermal conditions crystallization 40 hours, washing and filtering is also dried, then ammonium exchanges, dry, roasting, obtains catalyzer.Grain size is 2.1 microns.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1.5 grams of catalyzer, 50 grams of methyl alcohol, 30 grams of dme, 100 grams of formaldehyde, 100 DEG C and made pressure be 3MPa by inflated with nitrogen under react 6 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, reaction result is in table 1.
[embodiment 3]
By SiO 2: Al 2o 3: OH -: Cl -: H 2o=1:0.03:0.28:0.4:60.Take each material, aluminum nitrate is dissolved in distilled water, then drip silicon sol, stir 1 hour, then drip potassium chloride solution, stir 1 hour, then drip potassium hydroxide aqueous solution, then continue stirring 5 hours.Gained mixture crystallization 12 hours under 80 DEG C of hydrothermal conditions, then under 150 DEG C of hydrothermal conditions crystallization 50 hours, washing and filtering is also dried, then ammonium exchanges, dry, roasting, obtains catalyzer.Grain size is 1.8 microns.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1 gram of catalyzer, 80 grams of methyl alcohol, 100 grams of formaldehyde, 85 DEG C and made pressure be 1MPa by inflated with nitrogen under react 10 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, reaction result is in table 1.
[embodiment 4]
By SiO 2: Al 2o 3: OH -: Cl -: H 2o=1:0.009:0.3:0.4:60.Take each material, aluminum nitrate is dissolved in distilled water, then drip silicon sol, stir 1 hour, then drip sodium chloride aqueous solution, stir 1 hour, then drip potassium hydroxide aqueous solution, then continue stirring 5 hours.Gained mixture crystallization 12 hours under 90 DEG C of hydrothermal conditions, then under 180 DEG C of hydrothermal conditions crystallization 24 hours, washing and filtering is also dried, then ammonium exchanges, dry, roasting, obtains catalyzer.Grain size is 1 micron.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 0.9 gram of catalyzer, 50 grams of methyl alcohol, 30 grams of dme, 100 grams of formaldehyde, 120 DEG C and made pressure be 4MPa by inflated with nitrogen under react 5 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, reaction result is in table 1.
[comparative example 1]
By NaZSM-5 molecular screen primary powder (SiO 2/ Al 2o 3mol ratio is 70) within 5 hours, remove organic formwork agent 550 DEG C of roastings.Resulting materials exchanges 3 times at 80 DEG C with the aqueous ammonium nitrate solution of 10% weight content, washes 2 times, and 120 DEG C of dryings 10 hours, 550 DEG C of roastings 5 hours, obtain catalyzer.Grain size is 1 micron.
Catalyst performance examination is with [embodiment 1].Reaction result is in table 1.
[comparative example 2]
By NaZSM-5 molecular screen primary powder (SiO 2/ Al 2o 3mol ratio is 120) within 5 hours, remove organic formwork agent 550 DEG C of roastings.Resulting materials exchanges 3 times at 80 DEG C with the aqueous ammonium nitrate solution of 10% weight content, washes 2 times, and 120 DEG C of dryings 10 hours, 550 DEG C of roastings 5 hours, obtain catalyzer.Grain size is 10 microns.
Catalyst performance examination is with [embodiment 1].Reaction result is in table 1.
Table 1

Claims (3)

1. prepare the method for polymethoxy dimethyl ether for one kind, with methyl alcohol or dme and formaldehyde or trioxymethylene for raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.5 ~ 6, it is 70 ~ 150 DEG C in temperature of reaction, reaction pressure is under 0.5 ~ 6MPa condition, and reaction raw materials and ZSM-5 catalyst exposure generate polymethoxy dimethyl ether; Catalyst levels is 0.1 ~ 10% of reaction raw materials weight; ZSM-5 catalyzer wherein used is prepared as follows:
By silicon source, aluminium source, alkali source, Yanyuan and water mixing, reaction mixture is with molar ratio computing SiO 2: Al 2o 3: OH -: Cl -: H 2o=1:0.005 ~ 0.02:0.15 ~ 0.4:0.08 ~ 0.4:30 ~ 100; By said mixture 60 ~ 120 DEG C of crystallization 2 ~ 24 hours, then 140 ~ 200 DEG C of crystallization 2 ~ 72 hours, products therefrom through being separated, washing, dry, ammonium is handed over, after roasting, obtain described catalyzer; Wherein said silicon source is selected from least one in diatomite, water glass, silicon sol or White Carbon black, aluminium source is selected from least one in sodium metaaluminate, Tai-Ace S 150 or aluminum nitrate, alkali source is selected from least one in sodium hydroxide or potassium hydroxide, and Yanyuan is selected from least one in sodium-chlor or Repone K.
2. prepare the method for polymethoxy dimethyl ether according to claim 1, it is characterized in that the crystal grain diameter of ZSM-5 catalyzer is less than 3 microns.
3. prepare the method for polymethoxy dimethyl ether according to claim 1, it is characterized in that formaldehyde is the formaldehyde solution of 10 ~ 80wt%, or paraformaldehyde or trioxymethylene.
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CN107778149A (en) * 2016-08-26 2018-03-09 张也贤 The method for preparing polymethoxy dimethyl ether
CN106397142B (en) * 2016-09-05 2019-06-21 沈阳化工大学 A kind of highly selective method for preparing single dimerization dimethoxym ethane

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CN102040488A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Method for synthesizing PODE (polyformaldehyde dimethyl ether)

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1332114A (en) * 2001-06-28 2002-01-23 复旦大学 Optimized and oriented growth process of MFT-type zeolite crystal
CN101768058A (en) * 2009-01-07 2010-07-07 中国石油化工股份有限公司 Method for preparing polyoxymethylene dimethyl ether
CN102040491A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves
CN102040488A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Method for synthesizing PODE (polyformaldehyde dimethyl ether)

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