CN106362798A - Catalyst used in liquid phase technology to produce methylal - Google Patents
Catalyst used in liquid phase technology to produce methylal Download PDFInfo
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- CN106362798A CN106362798A CN201610544029.5A CN201610544029A CN106362798A CN 106362798 A CN106362798 A CN 106362798A CN 201610544029 A CN201610544029 A CN 201610544029A CN 106362798 A CN106362798 A CN 106362798A
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- catalyst
- oxygen
- methanol
- salt
- liquid phase
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst used in a liquid phase technology to produce methylal. Feed gas used in the invention can be oxygen, air or other oxygen-containing mixed gas. The Ru-based catalyst in the invention can be a nitrogen-containing organic ligand and Ru salt complex (with a molar ratio of the nitrogen-containing organic ligand to the Ru salt of 0-4), and the use concentration of the catalyst is 0.0001-0.1 g/ml. The general technology is characterized in that methanol, the oxygen-containing gas and the catalyst are added to a high temperature reaction kettle, and methylal is synthesized at a reaction temperature of 60-180 DEG C under a reaction pressure of 0.5-5 MPa.
Description
Technical field
The present invention relates to a kind of methanol and oxygen-containing gas are under the conditions of liquid phase process, a step oxidation generates the catalysis of dimethoxym ethane
Agent, belongs to chemical field.
Background technology
Dimethoxym ethane (methylal), chemical name is dimethoxymethane (dimethoxymethane, dmm), because having
Low toxicity, low boiling, good dissolubility and property compatible with water, are a kind of excellent environment-friendly type solvents, are also important chemical industry
Intermediate.Dimethoxym ethane has rich oxygen content, and the mass fraction of its oxygen is 42.1%, and no c-c key, is a kind of oil product of high potentiality
Additive.Add the dimethoxym ethane that mass fraction is 5%～10% in diesel oil, in-engine combustibility can be effectively improved,
Reduce the content of hc and co in emission, reduce environmental pollution.Dimethoxym ethane or a kind of Downstream Products of Methanol of high level, therefore
Exploitation dimethoxym ethane industry not only contributes to alleviate methanol production capacity surplus, simultaneously significant to environmental conservation.
The industrial at present method for producing dimethoxym ethane is methanol and stiasny method, including two steps: the first step is first
Alcohol generates formaldehyde under silver or iron-molybdic catalyst effect；Second step is that methanol generates first again with formaldehyde under acid catalyst effect
Acetal.This technique is the main technique that dimethoxym ethane produces now, comparative maturity, but there is reaction temperature height, catalyst activity
Relatively low and the problems such as equipment corrosion is serious, and technological process is complicated, leads to production cost to remain high.Therefore from economy and
Environmental conservation angle is set out, and domestic and international researcher is more and more interested in methanol one-step oxidation process dimethoxym ethane.
Aoxidize the research of formal catalyzer processed for methanol one step, majority concentrates in gas phase continuous processing, and here
Multiple catalyst systems are developed under process conditions.Researchers have investigated carrier loaded re base catalyst in catalysis methanol one
Performance difference in step oxidation dimethoxym ethane reaction.Comparatively re/tio2、re/γ-fe2o3Catalyst relatively has advantage, property
Can preferably, but the yield of dimethoxym ethane is not high, be not enough to prepare highly purified dimethoxym ethane product (yuan y z, liu h c,
Imoto h, et al.performance and characterization of a new crystalline sbre2o6
catalyst for selective oxidation of methanol to methylal[j].journal of
Catalysis, 2000.195 (1): 51-61.nikonova o a, capron m, fang g, et al.novel approach
to rhenium oxide catalysts for selective oxidation of methanol to dmm[j]
.journal of catalysis, 2011.279 (2): 310-318.).The research being directed to v base catalyst in recent years is relatively more,
Having investigated it and be supported on different structure tio of researchers' system2Catalytic performance difference on carrier, achieves better result.
Although v is cheap and easy to get, there is larger toxicity, be unfavorable for environmental conservation (zhao h, bennici s, shen j, et
al.calorimetric study of the acidic character of v2o5-tio2/so4 2-catalysts used
in methanol oxidation to dimethoxymethane[j].journal of thermal analysis and
Calorimetry, 2010.99 (3): 843-847.guo h q, li d b, chen c b, et al.one-step
oxidation of methanol to dimethoxymethane on v2o5/ceo2catalyst[j].chinese
Journal of catalysis, 2012.33 (5): 813-818.).Also have heteropoly acid through sio2Load is as this reaction
Catalyst, and with v is modified, there is higher dimethoxym ethane selectivity (zhang q d, tan y s, yang c h, et
al.mncl2modified h4siw12o40/sio2catalysts for catalytic oxidation of dimethy
Ether to dimethoxymethane [j] .journal of molecular catalysis a-chemical,
2007.263 (1-2): 149-155.).
And under the conditions of being used in liquid phase batch technology, methanol and oxygen one-step synthesize the catalyst that dimethoxym ethane processed reacts, at present
(Liu Peng, Deng Zhiyong, Yang Xiangui wait .cucl/ oxime complex catalysis methanol liquid to a kind of only copper containing n-donor ligand catalyst of report
The oxidation of phase one step generates dimethoxymethane [j]. gas chemical industry: cl chemistry and chemical industry .2013, (06): 16-19), this catalysis
Agent is higher to the selectivity of dimethoxym ethane, but catalyst life is poor.
Content of the invention
The present invention uses ru base catalyst, and methanol is contracted in liquid phase process condition next step oxidative synthesis first with oxygen-containing gas
Aldehyde.The ru base catalyst being used is ru salt and nitrogenous organic coordination compound, or only ru salt；Wherein containing n-donor ligand can be for having
With the bidentate of lower skeleton, multiple tooth nitrogen-containing compound:As 1，2-cyclohexanedionedioxime, glyoxime, diacetyldioxime
Deng compound and its their derivant；Ru salt can be the compound such as its halogenide, sulfate, nitrate.
General reactions condition of the present invention is: the containing n-donor ligand in catalyst is 0～4 with the mol ratio of ru salt, and catalyst is used
Amount 0.0001～0.1g/ml, temperature 60 C～180 DEG C, pressure 0.5mpa～5.0mpa.
Catalyst used in the present invention has prospects for commercial application.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated.
[embodiment 1] adds methanol 20ml (15.8g), hydrate ruthenium trichloride 0.1g, 1,2- in the high anti-reactor of 100ml
Cyclohexanedionedioxime 0.0171g；Use o2After air in replacement reaction kettle, it is re-filled with the o of 2.0mpa2；After pressure stability in kettle, open
Begin to stir (500r/min) and heat up, 110 DEG C of reaction temperature, response time 40min.Using gas chromatogram fixative, reaction is produced
Thing is analyzed, and the results are shown in Table 1.
[embodiment 2～4] changes usage amount, other conditions and [embodiment 1] identical, the product of 1，2-cyclohexanedionedioxime
Analysis result is listed in Table 1 below.
[embodiment 5] adds methanol 20ml (15.8g), hydrate ruthenium trichloride 0.1g in the high anti-reactor of 100ml；Use o2
After air in replacement reaction kettle, it is re-filled with the o of 2.0mpa2；After pressure stability in kettle, start to stir (500r/min) and heat up,
110 DEG C of reaction temperature, response time 40min.Using gas chromatogram fixative, product is analyzed, result is listed in table 1
In.
[embodiment 6～7] changes usage amount, other conditions and [embodiment 5] identical, the product analysis of hydrate ruthenium trichloride
The results are shown in Table 1.
[embodiment 8～9] changes the o being passed through in reactor2Pressure, other conditions and [embodiment 5] identical, product analysis
The results are shown in Table 1.
[embodiment 10～11] changes reaction temperature, and pressure is 3mpa, and other conditions are identical with [embodiment 5], and product divides
The results are shown in Table 1 for analysis.
The each embodiment product analysis result of table 1
Claims (6)
1. one kind is under the conditions of liquid phase process, the ru base catalyst of methanol and oxygen direct one-step synthesis dimethoxym ethane.
2. according to claim 1 it is characterised in that the unstripped gas being used can be oxygen, air and other oxygen-containing mixing
Gas.
3. ru base catalyst according to claim 1 is it is characterised in that ru salt is directly mixed with containing n-donor ligand or in advance
Complexation uses as catalyst；Wherein ru salt can be the compound such as its halogenide, sulfate, nitrate, and containing n-donor ligand is to have
With the bidentate of lower skeleton, multiple tooth nitrogen-containing compound:As 1，2-cyclohexanedionedioxime, glyoxime, diacetyl two
Oxime etc..
4. ru base catalyst according to claim 1 is it is characterised in that the containing n-donor ligand using is 0 with the mol ratio of ru salt
～4.
5. ru base catalyst according to claim 1 is it is characterised in that catalyst concentration is 0.0001～0.1g/
ml.
6. ru base catalyst according to claim 1 it is characterised in that reaction temperature be 60～180 DEG C, reaction pressure be
0.5～5mpa.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2015104564493 | 2015-07-24 | ||
| CN201510456449 | 2015-07-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106362798A true CN106362798A (en) | 2017-02-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN201610544029.5A Pending CN106362798A (en) | 2015-07-24 | 2016-07-12 | Catalyst used in liquid phase technology to produce methylal |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107413386A (en) * | 2017-08-21 | 2017-12-01 | 中国科学院成都有机化学有限公司 | A kind of catalyst of methanol liquid phase one-step oxidation to methylal and preparation method thereof and application method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634655A (en) * | 2004-11-26 | 2005-07-06 | 南京大学 | Catalyst for producing methylal by selective oxidation of methanol and preparation method and use thereof |
| CN101224431A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof |
| CN101396667A (en) * | 2007-09-28 | 2009-04-01 | 南京大学 | V2O5 composite catalyst loaded by Ce-V-Ti-O meso-material |
-
2016
- 2016-07-12 CN CN201610544029.5A patent/CN106362798A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634655A (en) * | 2004-11-26 | 2005-07-06 | 南京大学 | Catalyst for producing methylal by selective oxidation of methanol and preparation method and use thereof |
| CN101396667A (en) * | 2007-09-28 | 2009-04-01 | 南京大学 | V2O5 composite catalyst loaded by Ce-V-Ti-O meso-material |
| CN101224431A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof |
Non-Patent Citations (2)
| Title |
|---|
| MEILAN LI ET AL.: "Ruthenium trichloride as a new catalyst for selective production of dimethoxymethane from liquid methanol with molecular oxygen as sole oxidant", 《CATALYSIS COMMUNICATIONS》 * |
| 刘鹏等: "CuCl/肟配合物催化甲醇液相一步氧化生成二甲氧基甲烷", 《天然气化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107413386A (en) * | 2017-08-21 | 2017-12-01 | 中国科学院成都有机化学有限公司 | A kind of catalyst of methanol liquid phase one-step oxidation to methylal and preparation method thereof and application method |
| CN107413386B (en) * | 2017-08-21 | 2020-11-24 | 中国科学院成都有机化学有限公司 | Catalyst for synthesizing methylal by methanol liquid-phase one-step oxidation, and preparation method and use method thereof |
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