CN105884612B - A kind of method that methanol vapor phase dehydrogenation prepares methyl formate - Google Patents
A kind of method that methanol vapor phase dehydrogenation prepares methyl formate Download PDFInfo
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- CN105884612B CN105884612B CN201610232095.9A CN201610232095A CN105884612B CN 105884612 B CN105884612 B CN 105884612B CN 201610232095 A CN201610232095 A CN 201610232095A CN 105884612 B CN105884612 B CN 105884612B
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- catalyst
- methyl formate
- sba
- vapor phase
- methanol vapor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The present invention provides a kind of methods that methanol vapor phase dehydrogenation prepares methyl formate, include the following steps：Step 1 prepares 15 catalyst of Cu Co/SBA；Step 2, methanol vapor phase dehydrogenation prepare methyl formate：Methanol is entered to the fixed bed reactors progress gas phase reaction for being mounted with 15 catalyst of Cu Co/SBA prepared by step 1 after 200 DEG C of vaporizations, using N2 as carrier gas, reaction carries out under normal pressure, 200~280 DEG C of reaction temperature, product is collected in continuous sampling lh at a given temperature, ice-water bath condensation.15 bimetallic catalyst preparation processes of Cu Co/SBA are simple used by the notable feature of the present invention, have good catalytic activity and stability during the reaction.
Description
Technical field
The invention belongs to organic catalysis fields, refer in particular to a kind of method that methanol vapor phase dehydrogenation prepares methyl formate.
Background technology
Methyl formate is a kind of widely used low boiling point solvent, can be directly used as insecticide, fungicide and for handling
Cereal, fruit, dry fruit, tobacco fumigant.More importantly methyl formate or one kind " omnipotent intermediate ", can derive one
The compound of series, such as:Formic acid, acetic acid, n,N-Dimethylformamide, ethylene glycol, dimethyl carbonate etc. are widely used in medicine
With pesticide synthesis industry, increasingly it is taken seriously in C1 chemical fields.
Traditional methyl formate preparation method mainly has esterification process and methanol carbonylation.Esterification process is by formic acid and methanol
Methyl formate is synthesized by esterification, this method is needed using the concentrated sulfuric acid as catalyst, and technique falls behind, and consumes formic acid, equipment
Seriously corroded.Foreign countries have eliminated, and domestic individual small factories are still using.Methanol carbonylation is using methanol and carbon monoxide as raw material
Methyl formate is synthesized, the disadvantages of this method is the CO gas needed using absolute methanol and high-purity, causes this method
The production cost of methyl formate is higher.Methanol direct dehydrogenation method, which prepares methyl formate, has raw material single, and equipment investment is low, environment
It is friendly and can by-product hydrogen the advantages that, Southwestern China chemical research institute develops the commercial plant for producing 2kt per year, and methanol conversion is
30%-40%, methyl formate selectively reach 80% or so.As it can be seen that methanol oxidation dehydrogenation is prepared in methyl formate technique, methanol
The yield of conversion ratio and methyl formate is relatively low, researchs and develops new catalyst, to improve methyl formate one way to the maximum extent
Yield is still current research hotspot.
Invention content
The present invention is directed to develop a kind of high activity and highly selective catalyst, first is prepared for the direct catalytic dehydrogenation of methanol
Sour methyl esters.
The present invention is achieved through the following technical solutions：
A kind of method that methanol vapor phase dehydrogenation prepares methyl formate, includes the following steps：
Step 1 prepares Cu-Co/SBA-15 catalyst；
Step 2, methanol vapor phase dehydrogenation prepare methyl formate：Methanol is entered after 200 DEG C of vaporizations and is mounted with step 1 and prepares
Cu-Co/SBA-15 catalyst fixed bed reactors carry out gas phase reaction, with N2As carrier gas, reaction carries out under normal pressure,
Product is collected in 200~280 DEG C of reaction temperature, at a given temperature continuous sampling lh, ice-water bath condensation.
In step 1, in the Cu-Co/SBA-15 catalyst, the load quality score of Cu is 5wt%~20%wt, Co
Load quality score be 1wt%~5%wt, the granular size of the Cu-Co/SBA-15 catalyst is 40~60 mesh.
The preparation process of the Cu-Co/SBA-15 catalyst is：
Step A, the dipping volume for measuring carrier S BA-15 first, using Cu (NO3)2·3H2O is as copper source, Co
(NO3)2·6H2O as cobalt source according to the quality of catalyst than composition requirement, weigh Cu (NO3)2·3H2O and Co (NO3)2·
6H2O is configured to mixed aqueous solution, and carrier S BA-15 incipient impregnation 6h at normal temperatures are added；Sample is by dry, roasting after dipping
It burns, catalyst Precursors are made in tabletting.
Step B, catalyst Precursors in the gaseous mixture of nitrogen and hydrogen are carried out to reduction activation pretreatment, pressed in 0.1MPa
Under power, with 2 DEG C/min temperature programmings to 240 DEG C, H in this section of process gaseous mixture2Volume fraction is 10%, and gaseous mixture flow velocity is
250ml/min；Again with 1.0 DEG C/min temperature programmings to 300 DEG C, H during this2Volume fraction is adjusted to 30%, mixed airflow
Speed is 250ml/min, and 6h, the catalyst Cu-Co/SBA-15 after must restoring, the wherein load quality of Cu are restored in 300 DEG C of constant temperature
Score is 5wt%~20%wt, and the load quality score of Co is 1wt%~5%wt.
In step A, the drying, roasting, tabletting are to be dried overnight at 120 DEG C, and 550 DEG C of roasting 4h exist sample
10Mpa pressure lower sheetings, are sieved into the particle of 40~60 mesh.
In step 2, the fixed bed reactors are stainless steel tubular reactor, long 20cm, internal diameter 0.5cm.
In step 2, the Cu-Co/SBA-15 loaded catalysts are 3g.
In step 2, sample introduction the flow velocity 6mL/h, carrier gas N of methanol2Flow velocity is 30ml/min.
Advantageous effect：
Cu-Co/SBA-15 bimetallic catalyst preparation processes are simple used by the notable feature of the present invention, reacting
There is good catalytic activity and stability in journey；It is 0.5h in liquid phase air speed for example, using the catalyst of the present invention-1Left and right,
Normal pressure, under 260 DEG C of reaction conditions, the conversion per pass of methanol is up to 65%, and the selectivity of methyl formate reaches 70%.
Specific implementation mode
With reference to specific implementation example, the present invention will be further described：
Embodiment 1
The preparation of catalyst:
Cu-Co/SBA-15(Cu:Co:SBA-15=10:3:87, W/W) catalyst is prepared by equi-volume impregnating
's:The dipping volume of carrier S BA-15 is measured first；According to the composition requirement of catalyst, the raw material Cu of corrresponding quality is weighed
(NO3)2·3H2O, Co (NO3)2·6H2O and SBA-15 carries out incipient impregnation so that the mass content of Cu in catalyst sample
It is 3% for the mass content of 5%, Co, sample is dried overnight at 120 DEG C, 550 DEG C of roasting 4h, by sample under 10Mpa pressure
Tabletting is sieved into catalyst Precursors.
The activating pretreatment of catalyst：
Using fixed bed reactors, loaded catalyst 3g catalyst, feed ethanol enters stainless steel tube shape after gasification
Reactor (long 20cm, internal diameter 0.5cm) reacts；Before active testing, catalyst first uses H2-N2(10:90, V/V, 250ml/min)
Gaseous mixture carries out reduction activation, under 0.1MPa pressure, with 2 DEG C/min temperature programmings to 240 DEG C, and H in this section of process gaseous mixture2
Volume fraction is 10%；Again with 1.0 DEG C/min temperature programmings to 300 DEG C, H during this2Volume fraction is gradually adjusted to 30%,
6h is restored in 300 DEG C of constant temperature.
Methanol vapor phase dehydrogenation prepares methyl formate：
Under normal pressure by methanol with the rate of 6ml/h be transported to above-mentioned fixed bed reactors (fixed bed reactors be not
Become rusty steel tubular reactor, long 20cm, internal diameter 0.5cm) vaporizing chamber in, at 200 DEG C vaporize after enter reactor reaction, keep carry
Gas (N2) flow velocity be 30ml/min, investigate reaction temperature be respectively 200,220,240,260,280 DEG C, connect at a given temperature
Product is collected in continuous sampling lh, ice-water bath condensation, and the product and tail gas of condensation (equip FID respectively with two gas chromatographs respectively
With TCD detectors) it is analyzed, exhaust flow is demarcated with soap-foam flowmeter, and the result of test is listed in table 1 by calculating.
Table 1. Cu (5)-Co (3)/SBA-15 catalysis methanol dehydrogenation feed conversion ratios and reaction product selection
Embodiment 2
With embodiment 1, but change the load capacity of Cu and Co in catalyst, the load capacity of Cu and Co is made to distinguish by mass fraction
For 10% and 3%, acquired results are shown in Table 2.
Table 2. Cu (10)-Co (3)/SBA-15 catalysis methanol dehydrogenation feed conversion ratios and reaction product selection
Embodiment 3
With embodiment 1, but change the load capacity of Cu and Co in catalyst, the load capacity of Cu and Co is made to distinguish by mass fraction
For 20% and 3%, acquired results are shown in Table 3.
Table 3. Cu (20)-Co (3)/SBA-15 catalysis methanol dehydrogenation feed conversion ratios and reaction product selection
Embodiment 4
With embodiment 1, but change the load capacity of Cu and Co in catalyst, the load capacity of Cu and Co is made to distinguish by mass fraction
For 10% and 1%, acquired results are shown in Table 4.
Table 4. Cu (10)-Co (1)/SBA-15 catalysis methanol dehydrogenation feed conversion ratios and reaction product selection
Embodiment 5
With embodiment 1, but change the load capacity of Cu and Co in catalyst, the load capacity of Cu and Co is made to distinguish by mass fraction
For 10% and 5%, acquired results are shown in Table 5.
Table 5. Cu (10)-Co (5)/SBA-15 catalysis methanol dehydrogenation feed conversion ratios and reaction product selection
Claims (7)
1. a kind of method that methanol vapor phase dehydrogenation prepares methyl formate, which is characterized in that include the following steps：
Step 1 prepares Cu-Co/SBA-15 catalyst；
Step 2, methanol vapor phase dehydrogenation prepare methyl formate：Methanol is entered after 200 DEG C of vaporizations and is mounted with prepared by step 1
The fixed bed reactors of Cu-Co/SBA-15 catalyst carry out gas phase reaction, and using N2 as carrier gas, reaction carries out under normal pressure,
Product is collected in 200 ~ 280 DEG C of reaction temperature, at a given temperature continuous sampling lh, ice-water bath condensation.
2. the method that a kind of methanol vapor phase dehydrogenation according to claim 1 prepares methyl formate, which is characterized in that step 1
In, in the Cu-Co/SBA-15 catalyst, the load of Cu is 5wt% ~ 20wt%, and the load of Co is 1wt% ~ 5wt%, described
The granular size of Cu-Co/SBA -15 catalyst is 40 ~ 60 mesh.
3. the method that a kind of methanol vapor phase dehydrogenation according to claim 2 prepares methyl formate, which is characterized in that described
The preparation process of Cu-Co/SBA -15 catalyst is：
Step A, the dipping volume for measuring carrier S BA-15 first, using Cu (NO3)2 .3H2O is as copper source, Co (NO3)2·6H2O
As cobalt source Cu (NO are weighed than composition requirement according to the quality of catalyst3)2 .3H2O and Co (NO3)2·6H2O is configured to mix
Carrier S BA-15 incipient impregnation 6h at normal temperatures are added in aqueous solution；Sample is made and urges by dry, roasting, tabletting after dipping
Agent parent；
Step B, catalyst Precursors are carried out to reduction activation pretreatment in the gaseous mixture of nitrogen and hydrogen, in 0.1MPa pressure
Under, with 2 DEG C/min temperature programmings to 240 DEG C, H in this section of process gaseous mixture2Volume fraction is 10%, and gaseous mixture flow velocity is
250ml/min；Again with 1.0 DEG C/min temperature programmings to 300 DEG C, H during this2Volume fraction is adjusted to 30%, mixed airflow
Speed is 250ml/min, restores 6h, the catalyst Cu-Co/SBA-15 after must restoring in 300 DEG C of constant temperature, the wherein load of Cu is
The load of 5wt% ~ 20wt%, Co are 1wt% ~ 5wt%.
4. the method that a kind of methanol vapor phase dehydrogenation according to claim 3 prepares methyl formate, which is characterized in that step A
In, the drying, roasting, tabletting are to be dried overnight at 120 DEG C, 550 DEG C of roasting 4h, and sample is pushed in 10Mpa pressure
Piece is sieved into the particle of 40 ~ 60 mesh.
5. the method that a kind of methanol vapor phase dehydrogenation according to claim 1 prepares methyl formate, which is characterized in that step 2
In, the fixed bed reactors are stainless steel tubular reactor, long 20cm, internal diameter 0.5cm.
6. the method that a kind of methanol vapor phase dehydrogenation according to claim 1 prepares methyl formate, which is characterized in that step 2
In, the Cu-Co/SBA-15 loaded catalysts are 3g.
7. the method that a kind of methanol vapor phase dehydrogenation according to claim 1 prepares methyl formate, which is characterized in that step 2
In, sample introduction the flow velocity 6mL/h, carrier gas N of methanol2Flow velocity is 30ml/min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4480122A (en) * | 1982-09-27 | 1984-10-30 | Celanese Corporation | Process for producing methyl formate |
| CN102600879A (en) * | 2012-01-19 | 2012-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl formate and preparation method of catalyst for synthesizing methyl formate |
| CN103874677A (en) * | 2011-10-12 | 2014-06-18 | 格林尤格有限责任公司 | Ethyl acetate production |
| WO2014204200A1 (en) * | 2013-06-18 | 2014-12-24 | 서강대학교산학협력단 | Hydrogen fuel converter provided with photocatalyst and method for preparing hydrogen from methanol using photocatalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050059839A1 (en) * | 2003-09-15 | 2005-03-17 | The Regents Of The University Of California | Process and catalysts for the oxidation of methanol and/or ethanol |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4480122A (en) * | 1982-09-27 | 1984-10-30 | Celanese Corporation | Process for producing methyl formate |
| CN103874677A (en) * | 2011-10-12 | 2014-06-18 | 格林尤格有限责任公司 | Ethyl acetate production |
| CN102600879A (en) * | 2012-01-19 | 2012-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl formate and preparation method of catalyst for synthesizing methyl formate |
| WO2014204200A1 (en) * | 2013-06-18 | 2014-12-24 | 서강대학교산학협력단 | Hydrogen fuel converter provided with photocatalyst and method for preparing hydrogen from methanol using photocatalyst |
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Granted publication date: 20180821 Termination date: 20190414 |