CN100415371C - 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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- CN100415371C CN100415371C CNB2006100207074A CN200610020707A CN100415371C CN 100415371 C CN100415371 C CN 100415371C CN B2006100207074 A CNB2006100207074 A CN B2006100207074A CN 200610020707 A CN200610020707 A CN 200610020707A CN 100415371 C CN100415371 C CN 100415371C
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Abstract
The present invention discloses a catalyst system for synthesizing acetic anhydride through carbonylation under low pressure, which comprises rhodium-iodine-litium catalysts and organic ligands for increasing catalytic activity, wherein the content ratio (molar ratio) of the organic ligands and rhodium is from 0.5 to 100: 1, and the organic ligands comprise at least one kind of morpholine compounds, imidazole compounds and piperazine compounds or a mixture of at least two kinds of the three kinds of compounds. Due to the addition of organic ligands, the catalyst system can increase the catalytic activity in the carbonyl synthesis of acetic anhydride under low pressure.
Description
Technical field
The present invention relates to a kind of catalyst of methyl acetate synthesizing acetic anhydride by carbonyl under low pressure, specifically, is the catalyst 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 that organic ligand improves synthesizing acetic anhydride by carbonyl under low pressure catalytic reaction activity.
The catalyst of synthesizing acetic anhydride by carbonyl under low pressure of the present invention comprises rhodium-iodo-lithium catalyst, also contains the organic ligand that improves catalytic activity, and organic ligand is 0.5～100: 1 with the ratio (mol ratio) of the content of rhodium in the described catalyst, and described organic ligand comprises:
At least a morpholine kind compound with following general formula:
Wherein R is hydrogen, alkyl or acyl group;
Or be selected from imidazoles, 1,2-methylimidazole, 1, a kind of glyoxaline compound in 4-methylimidazole, N-methylimidazole, the N-ethyl imidazol(e);
Or the mixture of above-mentioned two compounds composition.
The preferred morpholine of wherein said morpholine kind compound, N-methylmorpholine, N-ethylmorpholine, N-N-formyl morpholine N-or N-acetyl morphine.
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 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 29lmol/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 (4)
1. the catalyst 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, the mol ratio of the content of organic ligand and rhodium is 0.5～100: 1 in the catalyst of described synthesizing acetic anhydride by carbonyl under low pressure, and described organic ligand comprises:
At least a morpholine kind compound with following general formula:
Wherein R is hydrogen, alkyl or acyl group;
Or be selected from imidazoles, 1,2-methylimidazole, 1, a kind of glyoxaline compound in 4-methylimidazole, N-methylimidazole, the N-ethyl imidazol(e);
Or the mixture of above-mentioned two compounds composition.
2. the catalyst 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 of synthesizing acetic anhydride by carbonyl under low pressure according to claim 1 is characterized in that, the mol ratio of the content of wherein said organic ligand and rhodium is 5～60: 1.
4. the catalyst of synthesizing acetic anhydride by carbonyl under low pressure according to claim 3 is characterized in that, the mol ratio of the content of wherein said organic ligand and rhodium is 10～30: 1.
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| CN100415371C true CN100415371C (en) | 2008-09-03 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
Citations (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 |
| CN1115688A (en) * | 1995-05-04 | 1996-01-31 | 中国科学院化学研究所 | Iminazoles-rhodium catalyst and its prepn |
| CN1740131A (en) * | 2005-09-06 | 2006-03-01 | 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
Patent Citations (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 |
| CN1115688A (en) * | 1995-05-04 | 1996-01-31 | 中国科学院化学研究所 | Iminazoles-rhodium catalyst and its prepn |
| CN1740131A (en) * | 2005-09-06 | 2006-03-01 | 西南化工研究设计院 | Low pressure methanol carboxylating process to synthesize acetic acid |
Non-Patent Citations (4)
| Title |
|---|
| 羰基合成醋酐过程中醋酸锂的作用. 陈群文.天然气化工，第26卷第1期. 2001 |
| 羰基合成醋酐过程中醋酸锂的作用. 陈群文.天然气化工，第26卷第1期. 2001 * |
| 非均相高分子铑催化剂在羰基合成醋酐工艺中的应用. 陈群文，叶明蓉.四川化工与腐蚀控制，第5卷第4期. 2002 |
| 非均相高分子铑催化剂在羰基合成醋酐工艺中的应用. 陈群文，叶明蓉.四川化工与腐蚀控制，第5卷第4期. 2002 * |
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