CN102000559B - Method for preparing dimethoxymethane by adopting supported niobium oxide catalyst - Google Patents
Method for preparing dimethoxymethane by adopting supported niobium oxide catalyst Download PDFInfo
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- CN102000559B CN102000559B CN2010105492324A CN201010549232A CN102000559B CN 102000559 B CN102000559 B CN 102000559B CN 2010105492324 A CN2010105492324 A CN 2010105492324A CN 201010549232 A CN201010549232 A CN 201010549232A CN 102000559 B CN102000559 B CN 102000559B
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Abstract
The invention discloses a method for preparing polyformaldehyde dimethyl ether by adopting a supported niobium oxide catalyst, which is characterized by comprising the following steps of: a) performing catalytic reaction to prepare the polyformaldehyde dimethyl ether, wherein a molar ratio of the dimethoxymethane to trioxymethylene is 0.5 to 5; supported niobium oxide is taken as a catalyst and accounts for 0.1 to 5 percent based on the total mass of reactants; the reaction temperature is between 100 and 200 DEG C; the time is between 10 minutes and 48 hours; and the reaction pressure is between 0.1 and 10MPa; b) performing rectification separation, namely separating a low-boiling point component dimethoxymethane DMM, polydiformaldehyde dimethyl ether DMM2 and the unreacted trioxymethylene, and separating polyformaldehyde diformaldehyde DMM3-8, wherein a kettle bottom is provided with high-polymerization degree polyformaldehyde dimethyl ether DMMn, and n is more than 8; and c) adding a small amount of fresh trioxymethylene into the dimethoxymethane, the diformaldehyde dimethyl ether DMM2 and the unreacted trioxymethylene which are separated in the step b and continuously reacting to prepare the polyformaldehyde diformaldehyde DMM3-8, which is suitable to be used as a diesel fuel-blended component so as to improve the utilization rate of the raw materials.
Description
Technical field:
The present invention relates to catalysis technical field, be a kind of method that adopts the load columbium oxide catalyst to prepare dimethoxym ethane; Particularly, be the method that in the presence of the load columbium oxide catalyst, prepares dimethoxym ethane by methyl alcohol and formaldehyde.
Background of invention:
Dimethoxym ethane is as a kind of important downstream product of formaldehyde, and its production method and application technology are all in constantly development and perfect.The today of especially being becoming tight in petroleum resources day; Dimethoxym ethane is as one of important spin-off of Coal Chemical Industry; Except that as the solvent, be widely used in fields such as methanol-based fuel, diesel fuel additives, fuel cell and liquid fuel, all caused extensive concern both domestic and external.
Laboratory initial preparation dimethoxym ethane is that formaldehyde, methyl alcohol add thermal synthesis in the presence of liquid acid such as the concentrated sulfuric acid.The industrial making method of dimethoxym ethane mainly comprises with the concentrated sulfuric acid to be methyl alcohol and the formaldehyde liquid phase condensation method of catalyst and to be the reaction rectification method of catalyst with the storng-acid cation exchange resin.As far back as 1993, it was catalyst that company of Asahi Chemical Industry just proposes in patent CN 1020450C with macropore or gel type cation exchanger resin, and it is seated in the auxiliary reactor, and the method through reactive distillation is the raw material synthesizing dimethoxym ethane with methyl alcohol, formalin.After this, the lot of domestic and foreign researchers are studied synthesizing dimethoxym ethane technology and catalyst.Proposing with HZSM-5 like CN 1301688A is catalyst, and methyl alcohol and formalin are the method for prepared in reaction dimethoxym ethane under 20~100 ℃ the condition in temperature in batch reactor.CN 101857533A proposes with SO
4-/SnO-ZrO
2-γ-Al
2O
3The method of producing methylal by composite solid-acid catalyst.It seems that comprehensively liquid phase condensation method production dimethoxym ethane is simple to operate, reaction condition is gentle, but all gets in the reactant liquor as the concentrated sulfuric acid of catalyst; Be difficult for separating from product; The acid of trace also can make product decompose, and produce a large amount of acid-bearing wastewater contaminated environment simultaneously, and dimethoxym ethane content is merely 85%~90% (mass fraction); Therefore, this method will be eliminated gradually.In the reaction rectification method, adopt the solid acid as catalyst, water insoluble, the preparation of product is carried out with separating simultaneously; Reduced follow-up separation equipment, reduced equipment investment cost, simultaneously; Solid acid can be recycled, and has also significantly reduced production cost, and the purity of the dimethoxym ethane that makes of this method is high; Generation waste water is few, and therefore, reaction rectification method has become the key industry production method of synthesizing dimethoxym ethane.
Present reaction rectification method synthesizing dimethoxym ethane mainly comprises two kinds of conventional catalyst rectification method and auxiliary reactor formula catalytic rectification processes.The conventional catalyst rectification method is that catalyst is seated in the rectifying column; The tower still is established reboiler; Cat head is established the condensation and collection device, and this technology will be reacted with these two aspects of separating of reactant mixture and is coupling in the tower and carry out, and has high-conversion rate, low energy consumption, easy to operate, advantage that investment of devices is few; But this method is catalyst changeout operation inconvenience more, and should not amplify on a large scale.Auxiliary reactor formula catalytic rectification process is that catalyst is placed the outer reactor of tower; Adopt pipeline that neighbouring or alternate column plate is imported and exported the unit equipment that links to each other with reactor; This method can be carried out catalyst regeneration or replacing under the situation of ordinary production, and the suitable engineering of carrying out is amplified.Therefore, at present large-scale dimethoxym ethane process units adopts auxiliary reactor formula catalytic rectification process more.Under the prerequisite that reactive distillation process finalizes the design almost, enhance productivity, must on existing basis, develop catalyst more efficiently.Experiment shows; The rising temperature and pressure helps being swift in response and carries out and balance is moved to right; But conventional resin catalyst all requires serviceability temperature to be lower than 100 ℃ usually, and therefore taking to load a large amount of resin catalysts usually or reduce the liquid air speed can have higher conversion ratio to generate dimethoxym ethane to guarantee methyl alcohol, formaldehyde.The presence of compound solid superacid catalyst agent has broken through the restriction of resin catalyst temperature, but the preparation method is complicated, and runs off easily in the liquid phase, and be restricted service life.
Summary of the invention:
The technical problem that the present invention will solve is to overcome in the past in the report; In the process of preparation dimethoxym ethane; Liquid acid catalyst etching apparatus, the contaminated environment used; The strong acid cation exchange resin catalyst serviceability temperature is lower, and conventional presence of compound solid superacid catalyst agent prepares the process complicacy, is prone to the shortcoming of loss, and a kind of method that is prepared dimethoxym ethane by load niobium oxide catalysis methanol and formolite reaction is provided.This catalyst system and catalyzing has good activity and selectivity, high stability, not etching apparatus, simple to operate, convenient separation, and the method for preparing catalyst characteristic of simple.In the use, can reduce the loadings of catalyst in the auxiliary reactor, being reflected under the high-speed of formaldehyde, methyl alcohol synthesizing dimethoxym ethane carried out.
The present invention is a kind of method that adopts the load columbium oxide catalyst to prepare dimethoxym ethane; It is characterized in that:
A) mol ratio of used methyl alcohol and formaldehyde is 1~10;
B) reaction temperature is 50~200 ℃, and the liquid air speed is 1~50hr
-1, reaction pressure is 0.1~1MPa.;
In this method, the load columbium oxide catalyst comprises the niobium of 0.01~20 weight %, and carrier is selected from one or more in aluminium oxide, silica, molecular sieve, magnesia, titanium oxide, zirconia, spinelle, mullite or the cordierite;
And prepare the load columbium oxide catalyst through following steps:
A) at first prepare organic niobium solution of 0.01~2 mol concentration: a certain amount of niobium source is dissolved in the organic acid soln; Obtain organic niobium solution; Said niobium source is selected from least a in niobic acid, halogenation niobium, the organic niobium, and organic niobium wherein is selected from niobium oxalate, acetic acid niobium, ethyoxyl niobium, isopropoxy niobium, butoxy niobium;
B) with organic niobium solution impregnating carrier, 80~200 ℃ of dryings;
C) under calcination atmosphere, calcination atmosphere is selected from a kind of in air, nitrogen, hydrogen, carbon dioxide, oxygen, ammonia, the steam, calcination steps b) infusion product; Sintering temperature is 300~1300 ℃, and the time is 1~24 hour, thereby obtains the load columbium oxide catalyst.
According to the method described in the present invention, it is characterized in that:
A) used methyl alcohol and formaldehyde mol ratio be 2~5;
B) reaction temperature is 100~150 ℃, and the liquid air speed is 5~20hr
-1, reaction pressure is 0.1~0.2MPa;
In this method, the load columbium oxide catalyst comprises the niobium of 0.02~15 weight %, and carrier is selected from a kind of in aluminium oxide, the silica;
And prepare the load columbium oxide catalyst through following steps:
A) at first prepare organic niobium solution of 0.02~1.8 mol concentration: a certain amount of niobium source is dissolved in the organic acid soln; Obtain organic niobium solution; Said niobium source is selected from least a in niobic acid, halogenation niobium, the organic niobium, and organic niobium wherein is selected from niobium oxalate, acetic acid niobium, ethyoxyl niobium, isopropoxy niobium, butoxy niobium;
B) with organic niobium solution impregnating carrier, 120~150 ℃ of dryings;
C) infusion product under air atmosphere, calcination steps b), sintering temperature is 500~1000 ℃, the time is 3~12 hours, thereby obtains the load columbium oxide catalyst.
The specific embodiment:
Embodiment 1
Under 50 ℃; With using distilled water washing in advance three times and being dissolved in the oxalic acid solution that mass concentration is 20% 200mL at the 7.1g of 120 ℃ of dried niobic acid; Obtain the niobium oxalate solution of 0.20mol/L, the activated alumina ball that adds φ 1.6~2.0mm of 320g subsequently carries out incipient impregnation while hot.Room temperature held 24 hours, 120 ℃ of dryings 24 hours in 550 ℃ of roastings 5 hours, obtain the niobium oxide load capacity and are 1.6% catalyst A under air atmosphere.
Embodiment 2
Under 50 ℃; With using distilled water washing in advance three times and being dissolved in the oxalic acid solution that mass concentration is 20% 200mL at the 9.3g of 120 ℃ of dried niobic acid; Obtain the niobium oxalate solution of 0.26mol/L, the activated alumina ball that adds φ 1.6~2.0mm of 320g subsequently carries out incipient impregnation while hot.Room temperature held 24 hours, 120 ℃ of dryings 24 hours in 550 ℃ of roastings 5 hours, obtain the niobium oxide load capacity and are 2.1% catalyst B under air atmosphere.
Embodiment 3
Under 50 ℃; With using distilled water washing in advance three times and being dissolved in the oxalic acid solution that mass concentration is 20% 200mL at the 3.1g of 120 ℃ of dried niobic acid; Obtain the niobium oxalate solution of 0.09mol/L, the activated alumina ball that adds φ 1.6~2.0mm of 320g subsequently carries out incipient impregnation while hot.Room temperature held 24 hours, 120 ℃ of dryings 24 hours in 550 ℃ of roastings 5 hours, obtain the niobium oxide load capacity and are 0.7% catalyst C under air atmosphere.
Embodiment 4
Under 50 ℃; With using distilled water washing in advance three times and being dissolved in the oxalic acid solution that mass concentration is 20% 200mL at the 8.3g of 120 ℃ of dried niobic acid; Obtain the niobium oxalate solution of 0.20mol/L, the silica spheres that adds φ 1.6~2.0mm of 380g subsequently carries out incipient impregnation while hot.Room temperature held 24 hours, 120 ℃ of dryings 24 hours in 550 ℃ of roastings 5 hours, obtain the niobium oxide load capacity and are 1.6% catalyst D under air atmosphere.
Embodiment 5
In the fixed bed reactors of tube inner diameter 12mm, loading catalyst A 100mL.Adopting oil bath to add the thermal control temperature of reactor is 120 ℃, and controlled pressure is 0.3MPa, and preparation formaldehyde mass concentration is 15.5%, and mol ratio is 1: 2.6 formaldehyde, a methanol aqueous solution, is 10.2hr by micro-feed pump control liquid air speed
-1Get into fixed bed reactors from end opening; Detection reaction liquid outlet temperature is collected product, recording reacting time after outlet temperature is stable after cooling; Methyl alcohol, dimethoxym ethane that timing sampling is analyzed in raw material and the product carry out qualitative, quantitative analysis by Agilent 7890A gas-chromatography; Formaldehyde carries out quantitative analysis by chemical titration, further calculates the yield of formaldehyde conversion ratio, dimethoxym ethane, and reaction result is listed in table 1.
Comparative example 1
Replace catalyst A with catalyst B, according to preparing dimethoxym ethane with embodiment 5 identical methods.Reaction result is listed in table 1.
Comparative example 2
Replace catalyst A with catalyst C, according to preparing dimethoxym ethane with embodiment 5 identical methods.Reaction result is listed in table 1.
Comparative example 3
Replace catalyst A with catalyst D, according to preparing dimethoxym ethane with embodiment 5 identical methods.Reaction result is listed in table 1.
Comparative example 4
Use catalyst A, the control oil bath temperature is 90 ℃, according to preparing dimethoxym ethane with embodiment 5 identical methods.Reaction result is listed in table 1.
Comparative example 5
Replace catalyst A with storng-acid cation exchange resin Amberlite 120B, the control oil bath temperature is 90 ℃, according to preparing dimethoxym ethane with embodiment 5 identical methods.Reaction result is listed in table 1.
The reaction result of table 1 preparation dimethoxym ethane
Catalyst | Reaction temperature (℃) | Formaldehyde conversion ratio % * | Dimethoxym ethane selectivity % ** | Dimethoxym ethane yield % *** |
Catalyst A | 120 | 61.25 | 98.94 | 60.60 |
Catalyst B | 120 | 65.32 | 98.72 | 64.48 |
Catalyst C | 120 | 60.36 | 99.15 | 59.85 |
Catalyst D | 120 | 55.82 | 98.25 | 54.84 |
Amberlite?120B | 90 | 50.87 | 99.17 | 50.44 |
Catalyst A | 90 | 50.32 | 99.32 | 49.98 |
*Formaldehyde conversion ratio=(in the 1-product in the amount/raw material of formaldehyde the amount of formaldehyde) * 100%
*Dimethoxym ethane selectivity=(changing into the formaldehyde amount of the formaldehyde amount/conversion of dimethoxym ethane) * 100%
* *Dimethoxym ethane yield=formaldehyde conversion ratio * dimethoxym ethane selectivity
Claims (2)
1. method that adopts the load columbium oxide catalyst to prepare dimethoxym ethane; It is characterized in that:
A) mol ratio of used methyl alcohol and formaldehyde is 1~10;
B) reaction temperature is 50~200 ℃, and the liquid air speed is 1~50hr
-1, reaction pressure is 0.1~1MPa;
In this method, the load columbium oxide catalyst comprises the niobium of 0.01~20 weight %, and carrier is selected from one or more in aluminium oxide, silica, molecular sieve, magnesia, titanium oxide, zirconia, spinelle, mullite or the cordierite;
And prepare the load columbium oxide catalyst through following steps:
A) at first prepare organic niobium solution of 0.01~2 mol concentration: a certain amount of niobium source is dissolved in the organic acid soln; Obtain organic niobium solution; Said niobium source is selected from least a in niobic acid, halogenation niobium, the organic niobium, and organic niobium wherein is selected from niobium oxalate, acetic acid niobium, ethyoxyl niobium, isopropoxy niobium, butoxy niobium;
B) with organic niobium solution impregnating carrier, 80~200 ℃ of dryings;
C) under calcination atmosphere, calcination atmosphere is selected from a kind of in air, nitrogen, hydrogen, carbon dioxide, oxygen, ammonia, the steam, calcination steps b) infusion product; Sintering temperature is 300~1300 ℃, and the time is 1~24 hour, thereby obtains the load columbium oxide catalyst.
2. according to the described method of claim 1, it is characterized in that:
A) used methyl alcohol and formaldehyde mol ratio be 2~5;
B) reaction temperature is 100~150 ℃, and the liquid air speed is 5~20hr
-1, reaction pressure is 0.1~0.2MPa;
In this method, the load columbium oxide catalyst comprises the niobium of 0.02~15 weight %, and carrier is selected from a kind of in aluminium oxide, the silica;
And prepare the load columbium oxide catalyst through following steps:
A) at first prepare organic niobium solution of 0.02~1.8 mol concentration: a certain amount of niobium source is dissolved in the organic acid soln; Obtain organic niobium solution; Said niobium source is selected from least a in niobic acid, halogenation niobium, the organic niobium, and organic niobium wherein is selected from niobium oxalate, acetic acid niobium, ethyoxyl niobium, isopropoxy niobium, butoxy niobium;
B) with organic niobium solution impregnating carrier, 120~150 ℃ of dryings;
C) infusion product under air atmosphere, calcination steps b), sintering temperature is 500~1000 ℃, the time is 3~12 hours, thereby obtains the load columbium oxide catalyst.
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CN103508860B (en) * | 2012-06-15 | 2015-07-15 | 华东理工大学 | Method for preparing polyoxymethylene dimethylethers from methanol and formaldehyde |
CN103508859B (en) * | 2012-06-15 | 2015-07-15 | 华东理工大学 | Method for preparing polyoxymethylene dimethyl ethers |
CN102824906B (en) * | 2012-09-07 | 2014-05-14 | 天津大学 | Loaded type molybdenum oxide catalyst for selectively oxidizing methanol to synthesize dimethoxymethane (DMM) and application |
CN104437598B (en) * | 2013-09-24 | 2017-07-14 | 中国石油化工股份有限公司 | Polyoxymethylene dimethyl ether ordered structure catalyst |
CN104152171B (en) * | 2014-07-24 | 2015-11-18 | 大连理工大学 | A kind of Catalytic lignin derives the method that aryl oxide prepares alkane liquid fuel |
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CN107021877A (en) * | 2017-05-09 | 2017-08-08 | 哈尔滨师范大学 | The method of methanol direct oxidation synthesizing dimethoxym ethane |
CN107442063B (en) * | 2017-07-25 | 2019-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of niobium modified activated aluminum oxide for purifying formaldehyde and application |
CN110508018B (en) * | 2019-09-03 | 2022-02-25 | 中国石油大学(华东) | Device and method for producing polymethoxy dimethyl ether |
CN112570011B (en) * | 2019-09-27 | 2023-07-21 | 中国石油化工股份有限公司 | Catalyst for preparing isosorbide and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1793036A (en) * | 2005-11-25 | 2006-06-28 | 北京工业大学 | Process for preparing potassium columbate K4Nb6O17 film |
US20070238608A1 (en) * | 2003-03-24 | 2007-10-11 | Saudi Basic Industries Corporation | Catalyst compostion for the selective conversion of alkanes to unsaturated carboxylic acids, method of making and method of using thereof |
CN101612560A (en) * | 2009-07-19 | 2009-12-30 | 桂林理工大学 | Compound oxide photocatalyst Bi 4M 2O 11Preparation method and application thereof |
US20090324468A1 (en) * | 2008-06-27 | 2009-12-31 | Golden Stephen J | Zero platinum group metal catalysts |
-
2010
- 2010-11-18 CN CN2010105492324A patent/CN102000559B/en not_active Expired - Fee Related
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070238608A1 (en) * | 2003-03-24 | 2007-10-11 | Saudi Basic Industries Corporation | Catalyst compostion for the selective conversion of alkanes to unsaturated carboxylic acids, method of making and method of using thereof |
CN1793036A (en) * | 2005-11-25 | 2006-06-28 | 北京工业大学 | Process for preparing potassium columbate K4Nb6O17 film |
US20090324468A1 (en) * | 2008-06-27 | 2009-12-31 | Golden Stephen J | Zero platinum group metal catalysts |
CN101612560A (en) * | 2009-07-19 | 2009-12-30 | 桂林理工大学 | Compound oxide photocatalyst Bi 4M 2O 11Preparation method and application thereof |
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