CN103508874B - A kind of method of iridium based compound catalyzed carbonylation legal system acetic acid - Google Patents
A kind of method of iridium based compound catalyzed carbonylation legal system acetic acid Download PDFInfo
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- CN103508874B CN103508874B CN201310402270.0A CN201310402270A CN103508874B CN 103508874 B CN103508874 B CN 103508874B CN 201310402270 A CN201310402270 A CN 201310402270A CN 103508874 B CN103508874 B CN 103508874B
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- based compound
- acetic acid
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- iridium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of method of iridium based compound catalyzed carbonylation legal system acetic acid, solve in the method for existing iridium based compound catalyzed carbonylation legal system acetic acid and need to use precious metal as promotor, the problem that production cost is high.The method adopts cyclopentadienyl carbonyl manganese as promotor; Having rewritten traditional technology can only use precious metal to make the history of promotor.
Description
Technical field
The present invention relates to the preparation method of acetic acid, particularly relate to the method for iridium based compound and methyl iodide catalysis methanol and reactive derivative carbonylation legal system acetic acid thereof.
Background technology
Acetic acid is important industrial chemicals, and it has multiple method to prepare.The method preparing acetic acid with promotor methyl iodide catalysis methanol and derivative carbonylation process thereof by rhodium, iridic compound is known.CN1191214A patent describes makes promotor with iridium based compound catalyzer, methyl iodide, to do promotor containing Ru, Os, Re etc., carries out continuous carbonylation acetic acid to methyl alcohol and its reactive derivative.The promotor that above-mentioned patented technology is mentioned is precious metal chemical complex, production cost can be increased during actual use, non-noble metal compound promotor how is used to substitute noble metal promoted agent, the important directions of innovation methyl alcohol and the research of reactive derivative carbonylation acetic acid thereof, especially necessary especially in the method using iridium carbonyl compound catalyzer acetic acid.
Summary of the invention
The object of the present invention is to provide improving one's methods of a kind of iridium based compound catalyzed carbonylation legal system acetic acid, the method adopts cyclopentadienyl carbonyl manganese to be promotor, and this promotor price is low, can reduce production cost accordingly.
For achieving the above object, the technical solution used in the present invention is: a kind of method of iridium based compound catalyzed carbonylation legal system acetic acid, is characterized in that: the method adopts cyclopentadienyl carbonyl manganese as promotor.
The concrete steps of aforesaid method are as follows:
(1) in zirconium material autoclave, acetic acid solvent, methyl alcohol or its reactive derivative, water, iridium based compound, methyl iodide, cyclopentadienyl carbonyl manganese is added;
(2), after using CO (carbon monoxide converter) gas replacement reaction kettle, being filled with carbon monoxide to reactor pressure is 3-4.5Mpa, and reacting by heating system, carries out carbonylation reaction.
In aforesaid method step (1), mn ion is 5-15 with the ratio of the amount of substance of iridium ion, preferred Mn/Ir=10.
Iridium based compound described in aforesaid method step (1) is IrCl
33H
2o, H
2irCl
6, [Ir (CO)
2i
2]
2, R
4n [Ir (CO)
2i
2], Ir (acac)
3or the one in iridium acetate, preferably without chlorine iridium based compound, more preferably containing the iridium based compound of iodine coordination.In the iridium based compound used, the valency of iridium can be+1 ,+3 or+4 valencys, and preferably+1 valency compound, is more preferably dissolved in+1 valency compound of acetic acid.In reaction solution, the concentration of iridium based compound is 500-5000ppm, preferred 1000-4000ppm, more preferably 1500-3000ppm.
Promotor methyl iodide in aforesaid method step (1), by its concentration 2-20% of percentage calculation of reactant gross weight, preferred 4-15%.
In aforesaid method step (2), temperature of reaction is 160
oc-210
oc, preferably 180
oc-200
oc, more preferably 190
oc ± 1.
The effect of invention: the present invention is directed to carbonylation of methanol and prepare acetic acid iridium based catalyst systems, invented application cyclopentadienyl carbonyl manganese as catalyzed reaction promotor, rewritten traditional technology and precious metal can only be used to make the history of promotor.
Embodiment
Experimental technique: the magnetic with temperature control unit is stirred zirconium material autoclave and is used for carbonylation experiment.Carbon monoxide source of the gas is top grade pure carbon monoxide steel cylinder.After experiment terminates, treat that temperature reduces to room temperature, release, gas is through cold organic solvent.With the gas chromatographic analysis liquid connecting fid detector.Acetic acid, methyl iodide peak is only had in reaction solution.
Speed of response is calculated as follows:
(molL
-1
h
-1
)=[(
n
raw material
÷
Δp
always
) ×
Δp] ÷ (V
reaction solution
× 60)
n raw material :the amount of substance mmol of the reaction raw materials that experiment drops into;
Δp
always :the Pressure Drop that the reaction raw materials complete reaction that experiment drops into will produce;
Δp:
the Pressure Drop that the reaction raw materials that experiment drops into produces at next minutes interval of specified pressure;
v reaction solution :the volume mL of the reaction raw materials that experiment drops into.
The present invention is further described below by concrete embodiment.
Example 1
Method of the present invention is illustrated by nonrestrictive typical embodiment below.
First group:
Control group:
Wherein Ir is Bu
4n [Ir (CO)
2i
2], Mn is CpMn (CO)
3, Ir:Mn=1:5, P=4.0Mpa.
Second group:
Control group:
Wherein Ir is Bu
4n [Ir (CO)
2i
2], Mn is CpMn (CO)
3, Ir:Mn=1:10, P=4.0Mpa.
Claims (7)
1. a method for iridium based compound catalyzed carbonylation legal system acetic acid, is characterized in that: the method adopts cyclopentadienyl carbonyl manganese as promotor.
2. the method for iridium based compound catalyzed carbonylation legal system acetic acid according to claim 1, is characterized in that: the concrete steps of the method are as follows:
(1) in zirconium material autoclave, acetic acid solvent, methyl alcohol or its reactive derivative, water, iridium based compound, methyl iodide, cyclopentadienyl carbonyl manganese is added;
(2), after using CO (carbon monoxide converter) gas replacement reaction kettle, being filled with carbon monoxide to reactor pressure is 3-4.5MPa, and reacting by heating system, carries out carbonylation reaction.
3. the method for iridium based compound catalyzed carbonylation legal system acetic acid according to claim 2, is characterized in that: in step (1), mn ion is 5-15 with the ratio of the amount of substance of iridium ion.
4. the method for iridium based compound catalyzed carbonylation legal system acetic acid according to claim 3, is characterized in that: mn ion is 10 with the ratio of the amount of substance of iridium ion.
5. the method for iridium based compound catalyzed carbonylation legal system acetic acid according to claim 2, is characterized in that: in step (1), the concentration of iridium based compound is 500-5000ppm.
6. the method for iridium based compound catalyzed carbonylation legal system acetic acid according to claim 5, is characterized in that: in step (1), the concentration of iridium based compound is 1000-4000ppm.
7. the method for iridium based compound catalyzed carbonylation legal system acetic acid according to claim 2, is characterized in that: promotor methyl iodide in step (1) is 2-20% by its concentration of percentage calculation of reactant gross weight.
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| CN201310402270.0A CN103508874B (en) | 2013-09-06 | 2013-09-06 | A kind of method of iridium based compound catalyzed carbonylation legal system acetic acid |
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| CN103508874B true CN103508874B (en) | 2016-01-20 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151983A (en) * | 1995-10-20 | 1997-06-18 | 英国石油化学品有限公司 | Process for production of acetic acid by carbonylation of dimethyl ether |
| CN1324341A (en) * | 1998-10-23 | 2001-11-28 | 国际人造丝公司 | Carbonylation of methanol in the presence of a rhodium/iridium/iodide ion catalytic system |
| CN101374794A (en) * | 2006-01-30 | 2009-02-25 | 英国石油化学品有限公司 | Process for the production of acetic acid |
-
2013
- 2013-09-06 CN CN201310402270.0A patent/CN103508874B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151983A (en) * | 1995-10-20 | 1997-06-18 | 英国石油化学品有限公司 | Process for production of acetic acid by carbonylation of dimethyl ether |
| CN1324341A (en) * | 1998-10-23 | 2001-11-28 | 国际人造丝公司 | Carbonylation of methanol in the presence of a rhodium/iridium/iodide ion catalytic system |
| CN101374794A (en) * | 2006-01-30 | 2009-02-25 | 英国石油化学品有限公司 | Process for the production of acetic acid |
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|---|---|
| CN103508874A (en) | 2014-01-15 |
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