CN106631802A - Method for preparing ethyl acetate through methanol carbonylation - Google Patents
Method for preparing ethyl acetate through methanol carbonylation Download PDFInfo
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- CN106631802A CN106631802A CN201611019563.0A CN201611019563A CN106631802A CN 106631802 A CN106631802 A CN 106631802A CN 201611019563 A CN201611019563 A CN 201611019563A CN 106631802 A CN106631802 A CN 106631802A
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- ethyl acetate
- catalyst
- ions
- organohalogen compounds
- hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of preparation of ethyl acetate, in particular to a method for preparing ethyl acetate through methanol carbonylation. The method comprises steps as follows: the temperature of a reactor is increased to 190-210 DEG C under the nitrogen atmosphere, and then nitrogen is introduced into the reactor; hydrogen and carbonic oxide are introduced into methanol containing organic halide, the components are heated by a preheater and mixed uniformly, feed gas is formed, passes a catalyst reactor accommodating a catalyst and is subjected to a reaction at reaction temperature of 50-850 DEG C, under the reaction pressure of 0.1-30 Mpa and at the gaseous hourly space velocity of 100-5,000 h<-1>, and ethyl acetate is obtained. According to the method, the catalyst and ethyl acetate are easy to separate, and pure methyl acetate can be directly prepared.
Description
（One）Technical field
The present invention relates to the preparation field of ethyl acetate, the method that more particularly to a kind of methanol carbonyl prepares ethyl acetate.
（Two）Background technology
Methyl acetate is a kind of Ester of small toxicity, without color, the fragrance with fruit.Its boiling point at ambient pressure
It is 57.8 DEG C, is one of current most widely used fatty acid ester, with excellent solubility property, not only widely should by people
Coating, ink, adhesive, medicine and pesticide intermediate field have been used, and it is required during many organic synthesis
One of intermediate reaction thing.
At present the main method of synthesis of acetic acid methyl esters has：（1）Methyl alcohol and the reaction rectification method that acetic acid is raw material；（2）With first
Alcohol is the methanol dehydrogenation synthetic method of raw material；（3）Methanol Carbonylation method with methyl alcohol and carbon monoxide as raw material；（4）Dimethyl ether carbonylation
Method；（5）The homologation of methyl formate.
Eastman Kodak Companies develop reactive distillation process：In the presence of acidic, acetic acid and methyl alcohol are anti-
Answer counter current contacting in rectifying column.Acetic acid is both reactant, and continuously removes product as extractant tower top, and tower reactor is continuously removed
Water.Because the esterification of acetic acid and methyl alcohol receives there is Data for Methyl Acetate-Methanol and methyl acetate-water in Equilibrium limit, and thing system
Two kinds of minimum azeotropic mixtures, therefore traditional process is sufficiently complex, needs multiple reactors and rectifying column.
Calendar year 2001 Kelkar etc. have studied methanol dehydrogenation oxonation on relatively inexpensive Fe-Sn composite catalysts.Its
In, these composite catalysts are included containing Fe and the salts substances containing Sn（Mainly organohalogen compounds）, and containing C, N, O, P or S
Etc. the compound of ligand, using itrile group compound or nitro compound as solvent.As a result show, the conversion ratio of acetic acid reaches
28.9%, the yield of methyl acetate has reached 24.1%.
Methanol Carbonylation method synthesis of acetic acid methyl esters, at present mainly two-step method, the i.e. methyl alcohol of industrial application is in Rh-I and Ir-
Synthesizing acetic acid by carbonylation in I catalyst system and catalyzings, acetic acid again with methanol esterification synthesis of acetic acid methyl esters.This method has obvious advantage,
Can by methanol production acetic acid, the acetic acid of generation can to carry out esterification with the methyl alcohol not reacted completely, such that it is able to
Generate methyl acetate.Because methyl acetate is difficult to separate with catalyst, it is more difficult to obtain pure chemical products.
（Three）The content of the invention
Defect in order to make up prior art of the invention, there is provided a kind of low cost, energy consumption are low, efficiency high, stay-in-grade first
The method that alcohol carbonylation prepares ethyl acetate.
The present invention is achieved through the following technical solutions：
A kind of method that methanol carbonyl prepares ethyl acetate, is characterized in that, comprise the following steps：
In a nitrogen atmosphere reactor is warmed up to into 190-210 DEG C, is then led to into nitrogen；To in the methyl alcohol containing organohalogen compounds
Hydrogen and carbon monoxide are passed through, being well mixed by preheater heating becomes anti-by the catalyst equipped with catalyst after unstripped gas
Device is answered, in reaction temperature 50-850 DEG C, reaction pressure 0.1-30Mpa, gas volume air speed 100-5000h-1Under conditions of react
At least 0.5 hour, you can obtain methyl acetate；
The mol ratio of methyl alcohol, organohalogen compounds, carbon monoxide and hydrogen is 1 wherein in unstripped gas：0.01-0.5：0.5-5：0.1-
10；
The organohalogen compounds are any one in organic chloride, organic bromide, organic iodide；The catalyst is copper
Zinc-aluminium is carrier and loads the catalyst of other metal promoters；
Described other metal promoters are any one in Pd ions, Cs ions, Mn ions, Mo ions, Cr ions；
The hydrogen-catalyst reactor is fixed bed reactors.
The organohalogen compounds are organic iodide.
Reaction temperature 100-500 DEG C, reaction pressure 1-10Mpa, gas volume air speed 500-2000h-1。
The organohalogen compounds are any one in dichloromethane, chloroethanes, methylene bromide, bromoethane, iodomethane.
The organohalogen compounds are iodomethane.
The invention has the beneficial effects as follows：
The present invention is to the methyl alcohol containing organohalogen compounds, CO and H2Unstripped gas by preheater heating be well mixed after, pass through
Equipped with copper zinc-aluminium it is carrier and loads the hydrogen-catalyst reactor of other metal promoters, in 50 ~ 850 DEG C of reaction temperature, reaction pressure
0.1 ~ 30MPa, the h of gas volume air speed 100 ~ 5000-1Lower reaction, catalyst is easily separated with ethyl acetate, and directly preparing to obtain
To pure methyl acetate.
（Four）Specific embodiment
It is below the specific embodiment of the present invention：
The mixing of unstripped gas：
Embodiment 1：Hydrogen and carbon monoxide are passed through in the methyl alcohol containing dichloromethane, raw material is mixed into by preheater heating
Gas, wherein methyl alcohol, organic chloride, the mol ratio of carbon monoxide and hydrogen are 1：0.01：0.5：0.1.
Embodiment 2：Hydrogen and carbon monoxide are passed through in the methyl alcohol containing chloroethanes, original is mixed into by preheater heating
Material gas, the wherein mol ratio of methyl alcohol, organic bromide, carbon monoxide and hydrogen are 1：0.5：5：10.
Embodiment 3：Hydrogen and carbon monoxide are passed through in the methyl alcohol containing methylene bromide, are mixed into by preheater heating
Unstripped gas, wherein methyl alcohol, organic iodide, the mol ratio of carbon monoxide and hydrogen are 1：0.01：5：0.1.
Embodiment 4：Hydrogen and carbon monoxide are passed through in the methyl alcohol containing bromoethane, original is mixed into by preheater heating
Material gas, the wherein mol ratio of methyl alcohol, organic chloride, carbon monoxide and hydrogen are 1：0.5：0.5：10.
Embodiment 5：Hydrogen and carbon monoxide are passed through in the methyl alcohol containing iodomethane, original is mixed into by preheater heating
Material gas, the wherein mol ratio of methyl alcohol, organic bromide, carbon monoxide and hydrogen are 1：0.1：1.5：5.
Embodiment 6：Hydrogen and carbon monoxide are passed through in the methyl alcohol containing iodomethane, original is mixed into by preheater heating
Material gas, the wherein mol ratio of methyl alcohol, organic iodide, carbon monoxide and hydrogen are 1：0.3：3：1.
In the above-described embodiments, dichloromethane, chloroethanes, methylene bromide, bromoethane, iodomethane can be replaced by arbitrarily
A kind of organic chloride, organic bromide, organic iodide.
Embodiment one：In a nitrogen atmosphere reactor is warmed up to into 190 DEG C, is then led to into nitrogen；By any of the above described one kind
Unstripped gas by equipped with copper zinc-aluminium be carrier and load Pd ions catalyst fixed bed reactors, 50 DEG C of reaction temperature,
Reaction pressure 0.1Mpa, gas volume air speed 100h-1Under conditions of react, obtain methyl acetate；After testing, methanol conversion is
31.3%, methyl acetate is selectively 86.5%.
Embodiment two：In a nitrogen atmosphere reactor is warmed up to into 210 DEG C, is then led to into nitrogen；By any of the above described one kind
Unstripped gas by the fixed bed reactors equipped with the catalyst that copper zinc-aluminium is carrier and load C s ion, 850 DEG C of reaction temperature,
Reaction pressure 30Mpa, gas volume air speed 5000h-1Under conditions of react, obtain methyl acetate；After testing, methanol conversion is
29.8%, methyl acetate is selectively 84.7%.
Embodiment three：In a nitrogen atmosphere reactor is warmed up to into 200 DEG C, is then led to into nitrogen；By any of the above described one kind
By the fixed bed reactors equipped with the catalyst that copper zinc-aluminium is carrier and load Mn ions after unstripped gas, in reaction temperature 100
DEG C, reaction pressure 1Mpa, gas volume air speed 500h-1Under conditions of react, obtain methyl acetate；After testing, methanol conversion
For 45.2%, methyl acetate is selectively 85.7%.
Example IV：In a nitrogen atmosphere reactor is warmed up to into 200 DEG C, is then led to into nitrogen；By any of the above described one kind
Unstripped gas by equipped with copper zinc-aluminium be carrier and load Mo ions catalyst fixed bed reactors, 500 DEG C of reaction temperature,
Reaction pressure 10Mpa, gas volume air speed 2000h-1Under conditions of react, obtain methyl acetate；After testing, methanol conversion is
51.6%, methyl acetate is selectively 55.4%.
Embodiment five：In a nitrogen atmosphere reactor is warmed up to into 200 DEG C, is then led to into nitrogen；To above-mentioned any one
Unstripped gas by the fixed bed reactors equipped with the catalyst that copper zinc-aluminium is carrier and load C r ion, 300 DEG C of reaction temperature,
Reaction pressure 20Mpa, gas volume air speed 4000h-1Under conditions of react, obtain methyl acetate.After testing, methanol conversion is
46.1%, methyl acetate is selectively 82.1%.
Embodiment six：In a nitrogen atmosphere reactor is warmed up to into 190 DEG C, is then led to into nitrogen；To above-mentioned any one
Unstripped gas is carrier by copper zinc-aluminium and loads the fixed bed reactors of the catalyst of Mn ions, in 850 DEG C of reaction temperature, reaction
Pressure 0.1Mpa, gas volume air speed 100h-1Under conditions of react, obtain methyl acetate.After testing, methanol conversion is
48.8%, methyl acetate is selectively 54.6%.
In addition to technical characteristic described in specification, remaining technical characteristic is technology known to those skilled in the art.
Claims (5)
1. a kind of method that methanol carbonyl prepares ethyl acetate, is characterized in that, comprise the following steps：
In a nitrogen atmosphere reactor is warmed up to into 190-210 DEG C, is then led to into nitrogen；To in the methyl alcohol containing organohalogen compounds
Hydrogen and carbon monoxide are passed through, being well mixed by preheater heating becomes anti-by the catalyst equipped with catalyst after unstripped gas
Device is answered, in reaction temperature 50-850 DEG C, reaction pressure 0.1-30Mpa, gas volume air speed 100-5000h-1Under conditions of react
At least 0.5 hour, you can obtain methyl acetate；
The mol ratio of methyl alcohol, organohalogen compounds, carbon monoxide and hydrogen is 1 wherein in unstripped gas：0.01-0.5：0.5-5：0.1-
10；
The organohalogen compounds are any one in organic chloride, organic bromide, organic iodide；The catalyst is copper
Zinc-aluminium is carrier and loads the catalyst of other metal promoters；
Described other metal promoters are any one in Pd ions, Cs ions, Mn ions, Mo ions, Cr ions；
The hydrogen-catalyst reactor is fixed bed reactors.
2. the method that methanol carbonyl according to claim 1 prepares ethyl acetate, is characterized in that, the organohalogen compounds
For organic iodide.
3. the method that methanol carbonyl according to claim 1 prepares ethyl acetate, is characterized in that, the reaction temperature
100-500 DEG C, reaction pressure 1-10Mpa, gas volume air speed 500-2000h-1。
4. the method that methanol carbonyl according to claim 1 prepares ethyl acetate, is characterized in that, the organohalogen compounds
For any one in dichloromethane, chloroethanes, methylene bromide, bromoethane, iodomethane.
5. the method that methanol carbonyl according to claim 4 prepares ethyl acetate, is characterized in that, the organohalogen compounds
For iodomethane.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1926085A (en) * | 2004-03-03 | 2007-03-07 | 英国石油化学品有限公司 | Process for producing carbonylation products |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1926085A (en) * | 2004-03-03 | 2007-03-07 | 英国石油化学品有限公司 | Process for producing carbonylation products |
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Application publication date: 20170510 |