CN1843624A - Catalyst system for synthesizing acetic anhydride by carbonyl under low pressure - Google Patents
Catalyst system for synthesizing acetic anhydride by carbonyl under low pressure Download PDFInfo
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- CN1843624A CN1843624A CN 200610020707 CN200610020707A CN1843624A CN 1843624 A CN1843624 A CN 1843624A CN 200610020707 CN200610020707 CN 200610020707 CN 200610020707 A CN200610020707 A CN 200610020707A CN 1843624 A CN1843624 A CN 1843624A
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Abstract
The invention discloses a catalyst used in composing acetic anhydride with low-pressure carbonyl. It comprises a rhodium-iodine-lithium catalyst and an organic ligand for improving the catalytic activity. The mol ratio between the organic ligand and the rhodium is 0.5-100:1; and said organic ligand comprises at least one of morpholine compound, imidazole compound and piperazine compound, or the mixture of at least two compounds.
Description
Technical field
The present invention relates to a kind of catalyst system of methyl acetate synthesizing acetic anhydride by carbonyl under low pressure, specifically, is the catalyst system that comprises rhodium-iodo-lithium.
Background technology
Aceticanhydride is a kind of derivative of acetic acid, is mainly used in the production cellulose acetate, also is widely used in medicine, dyestuff, agricultural chemicals and perfume industry, is one of important fine chemical material.The production capacity of the existing aceticanhydride of China is 15.5 tons/year, nearly 15～160,000 tons/year of the market has openings of domestic aceticanhydride.At present, oxo synthesis is the developing direction that aceticanhydride is produced.Wherein, the synthetic aceticanhydride of methyl acetate and carbon monoxide low pressure carbonylation is main production technology.Catalyst in this technology comprises rhodium-iodo-lithium system, and wherein rhodium is rhodium-containing compounds such as iodate rhodium, radium chloride, and iodine is iodomethane, and lithium is lithium iodide or lithium acetate.For improving the output of this production technology, be necessary to improve the activity of catalyst system in this production technology.
Summary of the invention
Thereby the technical problem to be solved in the present invention provides a kind of by adding the catalyst system that organic ligand improves synthesizing acetic anhydride by carbonyl under low pressure catalytic reaction activity.
The catalyst system of synthesizing acetic anhydride by carbonyl under low pressure of the present invention, comprise rhodium-iodo-lithium catalyst, also contain the organic ligand that improves catalytic activity, organic ligand is 0.5～100: 1 with the ratio (mol ratio) of the content of rhodium in the described catalyst system, and described organic ligand comprises:
At least a morpholine kind compound with following general formula:
Wherein R is hydrogen, alkyl or acyl group;
Or at least a glyoxaline compound with following general formula:
R wherein
1, R
2And R
3The hydrogen or alkyl of respectively doing for oneself;
Or at least a piperazine compounds with following general formula:
R wherein
1And R
2The hydrogen or alkyl of respectively doing for oneself; Or the mixture that at least two compounds are formed in above-mentioned three compounds.
The preferred morpholine of wherein said morpholine kind compound, N-methylmorpholine, N-ethylmorpholine, N-N-formyl morpholine N-or N-acetyl morphine.
The preferred imidazoles of wherein said glyoxaline compound, 1,2-methylimidazole, 1,4-methylimidazole, N-methylimidazole or N-ethyl imidazol(e).
The preferred piperazine of wherein said piperazine compounds, N methyl piperazine, N-ethyl piperazidine, N, N '-lupetazin or N, N '-diethyl piperazine.
The ratio of wherein said organic ligand and the content of rhodium preferred (mol ratio) is 5～60: 1, more preferably 10～30: 1.
Can improve the catalytic activity of synthesizing acetic anhydride by carbonyl under low pressure reacting middle catalyst system by adding above-mentioned organic ligand, promptly improve the per hour amount of aceticanhydride that every mole of rhodium generates, thereby can improve the output of this reaction system aceticanhydride.
The present invention is further detailed explanation below in conjunction with the embodiment in the specific embodiment.
The specific embodiment
Blank assay
In iodate rhodium-iodomethane-lithium acetate catalyst system and catalyzing, do not add any organic ligand, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, reaction obtained the mix products of aceticanhydride and acetic acid in 4.5 hours, and the catalytic activity of catalyst is 250mol/molRhh.
Embodiment 1
In iodate rhodium-iodomethane-lithium acetate catalyst system and catalyzing, add N-methylmorpholine, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, N-methylmorpholine is 14: 1 (mol ratios with the ratio of rhodium content, down together), reaction obtained the mix products of aceticanhydride and acetic acid in 2 hours, and the catalytic activity of catalyst is 329mol/molRhh.
Embodiment 2
In radium chloride-iodomethane-lithium acetate catalyst system and catalyzing, add morpholine, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, morpholine is 14: 1 with the ratio of rhodium content, reaction obtained the mix products of aceticanhydride and acetic acid in 2 hours, and the catalytic activity of catalyst is 320mol/molRhh.
Embodiment 3
In iodate rhodium-iodomethane-lithium iodide catalyst system and catalyzing, add imidazoles, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, imidazoles is 56: 1 with the ratio of rhodium content, reaction obtained the mix products of aceticanhydride and acetic acid in 3.5 hours, and the catalytic activity of catalyst is 372mol/molRhh.
Embodiment 4
In iodate rhodium-iodomethane-lithium acetate catalyst system and catalyzing, add 1, the 2-methylimidazole, at 180～190 ℃, 3.0～5.0Mpa, under 600～1000ppm rhodium concentration condition, 1, the 2-methylimidazole is 72: 1 with the ratio of rhodium content, reaction obtained the mix products of aceticanhydride and acetic acid in 3.25 hours, and the catalytic activity of catalyst is 347mol/molRhh.
Embodiment 5
In radium chloride-iodomethane-lithium iodide catalyst system and catalyzing, add imidazoles and N-methylmorpholine, the ratio of the content of imidazoles and N-methylmorpholine is 1.5: 1, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, the total amount of imidazoles and N-methylmorpholine is 16: 1 with the ratio of rhodium content, and reaction obtained the mix products of aceticanhydride and acetic acid in 3 hours, and the catalytic activity of catalyst is 328mol/molRhh.
Embodiment 6
In iodate rhodium-iodomethane-lithium acetate catalyst system and catalyzing, add imidazoles and N-methylmorpholine, the ratio of the content of imidazoles and N-methylmorpholine is 0.5: 1, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, the total amount of imidazoles and N-methylmorpholine is 20: 1 with the ratio of rhodium content, and reaction obtained the mix products of aceticanhydride and acetic acid in 2.5 hours, and the catalytic activity of catalyst is 350mol/molRhh.
Embodiment 7
In iodate rhodium-iodomethane-lithium acetate catalyst system and catalyzing, add imidazoles and N-methylmorpholine, the ratio of the content of imidazoles and N-methylmorpholine is 0.3: 1, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, the total amount of imidazoles and N-methylmorpholine is 28: 1 with the ratio of rhodium content, and reaction obtained the mix products of aceticanhydride and acetic acid in 2 hours, and the catalytic activity of catalyst is 350mol/molRhh.
Embodiment 8
In iodate rhodium-iodomethane-lithium acetate catalyst system and catalyzing, add imidazoles and N-methylmorpholine, the ratio of the content of imidazoles and N-methylmorpholine is 0.5: 1, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, the total amount of imidazoles and N-methylmorpholine is 20: 1 with the ratio of rhodium content, and reaction obtained the mix products of aceticanhydride and acetic acid in 2 hours, and the catalytic activity of catalyst is 425mol/molRhh.
Embodiment 9
In iodate rhodium-iodomethane-lithium acetate catalyst system and catalyzing, add imidazoles and N-methylmorpholine, the ratio of the content of imidazoles and N-methylmorpholine is 0.5: 1, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, the total amount of imidazoles and N-methylmorpholine is 23: 1 with the ratio of rhodium content, and reaction obtained the mix products of aceticanhydride and acetic acid in 2 hours, and the catalytic activity of catalyst is 374mol/molRhh.
Embodiment 10
In iodate rhodium-iodomethane-lithium acetate catalyst system and catalyzing, add imidazoles and N-methylmorpholine, the ratio of the content of imidazoles and N-methylmorpholine is 1.5: 1, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, the total amount of imidazoles and N-methylmorpholine is 11: 1 with the ratio of rhodium content, and reaction obtained the mix products of aceticanhydride and acetic acid in 2 hours, and the catalytic activity of catalyst is 291mol/molRhh.
Embodiment 11
In iodate rhodium-iodomethane-lithium acetate catalyst system and catalyzing, add imidazoles and N-methylmorpholine, the ratio of the content of imidazoles and N-methylmorpholine is 0.7: 1, at 180～190 ℃, 3.0～5.0Mpa, carry out the methyl acetate carbonylation under 600～1000ppm rhodium concentration condition, the total amount of imidazoles and N-methylmorpholine is 23: 1 with the ratio of rhodium content, and reaction obtained the mix products of aceticanhydride and acetic acid in 2 hours, and the catalytic activity of catalyst is 351mol/molRhh.
Embodiment result shows, add organic ligand of the present invention after, the activity of catalyst system and catalyzing is improved significantly.In addition, this caltalyst ties up to static placement two weeks in the air, does not see the obvious sediment phenomenon, illustrates that the stability of this catalyst system strengthens.After having added organic ligand of the present invention in the reactant liquor, under the heating evaporation condition catalyst system heat endurance significantly strengthen when also not having organic ligand.
Claims (6)
1. the catalyst system of synthesizing acetic anhydride by carbonyl under low pressure, comprise rhodium-iodo-lithium catalyst, it is characterized in that, also contain the organic ligand that improves catalytic activity, organic ligand is 0.5～100: 1 with the ratio (mol ratio) of the content of rhodium in the described catalyst system, and described organic ligand comprises:
At least a morpholine kind compound with following general formula:
Wherein R is hydrogen, alkyl or acyl group;
Or at least a glyoxaline compound with following general formula:
R wherein
1, R
2And R
3The hydrogen or alkyl of respectively doing for oneself;
Or at least a piperazine compounds with following general formula:
R wherein
1And R
2The hydrogen or alkyl of respectively doing for oneself; Or the mixture that at least two compounds are formed in above-mentioned three compounds.
2. the catalyst system of synthesizing acetic anhydride by carbonyl under low pressure according to claim 1 is characterized in that, wherein said morpholine kind compound is morpholine, N-methylmorpholine, N-ethylmorpholine, N-N-formyl morpholine N-or N-acetyl morphine.
3. the catalyst system of synthesizing acetic anhydride by carbonyl under low pressure according to claim 1 is characterized in that, wherein said glyoxaline compound is an imidazoles, 1,2-methylimidazole, 1,4-methylimidazole, N-methylimidazole or N-ethyl imidazol(e).
4. the catalyst system of synthesizing acetic anhydride by carbonyl under low pressure according to claim 1 is characterized in that, wherein said piperazine compounds is piperazine, N methyl piperazine, N-ethyl piperazidine, N, N '-lupetazin or N, N '-diethyl piperazine.
5. the catalyst system of synthesizing acetic anhydride by carbonyl under low pressure according to claim 1 is characterized in that, wherein said organic ligand is 5～60: 1 with the ratio (mol ratio) of the content of rhodium.
The catalyst system of 6 synthesizing acetic anhydride by carbonyl under low pressure according to claim 5 is characterized in that, wherein said organic ligand is 10～30: 1 with the ratio (mol ratio) of the content of rhodium.
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| CNB2006100207074A CN100415371C (en) | 2006-04-13 | 2006-04-13 | Catalyst system for synthesizing acetic anhydride by carbonyl under low pressure |
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| CNB2006100207074A CN100415371C (en) | 2006-04-13 | 2006-04-13 | Catalyst system for synthesizing acetic anhydride by carbonyl under low pressure |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476988A (en) * | 2010-11-22 | 2012-05-30 | 中国石油化学工业开发股份有限公司 | Method for preparing carboxyl anhydride |
| CN103896748A (en) * | 2014-04-04 | 2014-07-02 | 西南化工研究设计院有限公司 | Application of rhodium catalyst and aldehyde production method using same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328125A (en) * | 1979-05-14 | 1982-05-04 | University Of Illinois Foundation | Heterogeneous anionic transition metal catalysts |
| CN1037584C (en) * | 1995-05-04 | 1998-03-04 | 中国科学院化学研究所 | Iminazoles-rhodium catalyst and its prepn |
| CN100393689C (en) * | 2005-09-06 | 2008-06-11 | 西南化工研究设计院 | Low pressure methanol carboxylating process to synthesize acetic acid |
-
2006
- 2006-04-13 CN CNB2006100207074A patent/CN100415371C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476988A (en) * | 2010-11-22 | 2012-05-30 | 中国石油化学工业开发股份有限公司 | Method for preparing carboxyl anhydride |
| CN103896748A (en) * | 2014-04-04 | 2014-07-02 | 西南化工研究设计院有限公司 | Application of rhodium catalyst and aldehyde production method using same |
| CN103896748B (en) * | 2014-04-04 | 2015-11-04 | 西南化工研究设计院有限公司 | A kind of purposes of rhodium catalyst and adopt the method for this Catalyst Production aldehyde |
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| CN100415371C (en) | 2008-09-03 |
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Address after: 445 box 610255, South Airport Road, Sichuan, Chengdu, Chengdu Patentee after: Southwest Chemical Research & Design Institute Co., Ltd. Address before: 445 box 610255, South Airport Road, Sichuan, Chengdu, Chengdu Patentee before: Xinan Chemical Research & Design Inst. |