CN1212197C - Catalytic system used for homogeneous hydroxylation reaction and its manufacturing method and application - Google Patents
Catalytic system used for homogeneous hydroxylation reaction and its manufacturing method and application Download PDFInfo
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- CN1212197C CN1212197C CN 03102770 CN03102770A CN1212197C CN 1212197 C CN1212197 C CN 1212197C CN 03102770 CN03102770 CN 03102770 CN 03102770 A CN03102770 A CN 03102770A CN 1212197 C CN1212197 C CN 1212197C
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Abstract
The present invention relates to a catalytic system for homogeneous phase carbonylation reaction, which is composed of a main catalyst, a cocatalyst, an additive and a polar solvent, wherein the main catalyst has a chelate type square plane structure with double tooth coordination using N and O as coordination atoms, has the coordination center of rhodium acetate or rhodium nitrate, and potassium metal bonding with carboxylic acid in an ionic form; the cocatalyst is methyl iodide; the additive is lithium iodide, potassium iodide or lithium acetate dihydrate; the polar solvent is acetic acid glacial, acetic anhydride, methyl acetate or water. The present invention has the preparation steps: pyridinecarboxylic acid and potassium hydroxide monohydrate are dissolved in methanol or water solution so as to obtain an organic potassium ligand; rhodiumsolution is added in dissolved water or methanol solution so as to obtain a homogeneous bimetallic catalyst with small molecules. The catalytic system can be used in methanol carbonylation reaction for preparing acetic acid and methyl acetate carbonylation reaction for preparing acetic anhydride.
Description
Technical field
The present invention relates to a kind of catalyst system that is used for homogeneous carbonylation reaction.
The invention still further relates to the preparation method of Primary Catalysts in the above-mentioned catalyst system.
The present invention also relates to the application of above-mentioned catalyst system in methanol carbonylation and acetate carbonyl reaction.
Background technology
Since the seventies, low-pressure process methanol carbonyl synthesis of acetic acid technology has successfully been invented by U.S. Monsanto Company, has just progressively replaced two-step process such as ethylene process, makes acetate industry obtain fast development.The catalyst active center that this method adopts is a dicarbapentaborane diiodo-rhodium, as [Rh (CO)
2I
2]
-N
+R
4, [Roth, J.F.et al.Chem.Technol., 1971,600], this class title complex is very unstable in reaction process, very easily is converted into dicarbapentaborane tetraiodo rhodium [Rh (CO)
2I
4]
-N
+R
4And lose catalytic activity, therefore for keeping the stable of catalyst active center, except the certain CO dividing potential drop of necessary maintenance, also must in system, add a large amount of hydroiodic acid HIs and other complementary solvents, the corrodibility of reaction is sharply increased, also very harsh to the requirement of reaction material.
In order to improve this present situation, many research workers propose to change the homogeneous phase method into heterogeneous method, be Recent study a lot of be the rhodium catalyst series of part with the superpolymer, as being that the polymkeric substance that monomer makes is the rhodium complex catalyst of part with 4-vinylpyridine and vinylbenzene, its stability is [EP567331 better, 27 Oct 1993], but the solvability of this type of catalyzer is bad, makes reactive activity not ideal enough.
There are some research reports to propose to adopt gas solid method, being about to catalyst active center loads on the solid carrier, under certain temperature and pressure, the mixture of methyl alcohol, methyl iodide and carbon monoxide is passed through fixed bed catalyst, but this technology need consume a large amount of promotor methyl iodide, and is higher owing to temperature in the reaction process, easily carbon distribution, cause problems such as catalyst deactivation, rhodium loss, also can't realize industrialization.
Also have some research reports to propose in system, to add some small molecules, such as organic derivative, perhaps some metallic salts, the effect of finding pyridines, amine, lithium salts, sylvite is better, activity of such catalysts and stability are improved to some extent, and wherein sylvite has good result to the raising of catalyst stability.
Summary of the invention
The object of the present invention is to provide a kind of catalyst system that is used for homogeneous carbonylation reaction.
Another object of the present invention is to provide the preparation method of Primary Catalysts in a kind of above-mentioned catalyst system.
Catalyst system provided by the invention is made up of Primary Catalysts, promotor and additive, and wherein the Primary Catalysts structural formula is:
R is H or carboxylic hydrocarbon derivative in the formula; X is OAc
-Or NO
3 -, m is 2 or 3, n is 0,1 or 2.
Promotor is meant methyl iodide, and additive is lithium iodide, potassiumiodide or lithium acetate.
The preparation method of Primary Catalysts of the present invention is to be part with pyridine carboxylic acid sylvite, forms bimetal complexes with rhodium acetate or rhodium nitrate.Wherein said pyridine carboxylic acid sylvite is meant the sylvite of the pyridine derivate that contains carboxyl, and its ligand structure is as follows:
R is H or carboxylic hydrocarbon derivative in the formula, and n is 0,1 or 2.Wherein, preferably R is H, for example, and pyridine-2-potassium formiate, Nicotinicum Acidum potassium, pyridine-4-potassium formiate, pyridine-2-potassium acetate, pyridine-3-potassium acetate, pyridine-4-potassium acetate or than pyridine-3-potassium propionate etc.
Say that in more detail the preparation method of Primary Catalysts of the present invention is:
A) preparation of organo-metallic potassium part
One water potassium hydroxide of the pyridine carboxylic acid of 1 molar part and 1～10 molar part is dissolved in the methyl alcohol or the aqueous solution of 10～100 molar part, under agitation reacts 10～60 minutes, with excessive ether sedimentation, filtration, wash, be drying to obtain.
B) preparation of rhodium-potassium bimetal complexes
The part of 1 molar part is dissolved in the water or methanol solution of 10～100 molar part, be dissolved with the water or the methanol solution of 0.01～1 molar part rhodium acetate or rhodium nitrate 0～50 ℃ of dropping, the mol ratio of water or methyl alcohol and rhodium acetate or rhodium nitrate is 50～200: 1, after dropwising, isothermal reaction 10～120 minutes can obtain homogeneous small molecules bimetallic catalyst with excessive ether washing, filtration, drying.
Pyridine carboxylic acid of the present invention is: pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, pyridine-2-acetate, pyridine-3-acetate, pyridine-4-acetate or pyridine-3-propionic acid.
Primary Catalysts of the present invention has following technical characterictic:
1, the chela of double coordination and type square plane rhodium-potassium bimetal complexes, its part is a pyridine carboxylic acid sylvite, N wherein, the O atom forms the strong and weak different keys of joining with rhodium atom, the N atom is very strong donor atom, the electron binding energy 1ev that significantly raise in the coordination process, it is highly stable that the N → Rh that forms with rhodium joins key, and the electron binding energy rising amplitude of O atom is less, have only about 0.5ev, be more weak donor atom, behind rhodium formation O → Rh key, in reaction process, be easy to disassociation, make rhodium atom be in the coordination undersaturated condition, help the addition of promotor methyl iodide, the weak coordination Sauerstoffatom of dissociative is owing to the existence of chelating chain is strapped in the coordination scope of rhodium atom, after the oxidation addition process of methyl iodide is finished, again can be rapidly and the rhodium atom relocation bit, show good catalytic activity and stability.
2, because the active centre of Primary Catalysts of the present invention is rhodium acetate or rhodium nitrate, make that the mutual solubility of it and polarizable medium is better, the corresponding solubleness of active centre rhodium in reaction medium that increased, and then improve its reactive behavior, and this coordination structure is stable in reaction process, and the raising of rhodium concentration does not cause sedimentary increase.
3, because Primary Catalysts of the present invention is a bimetallic catalyst, it is the active centre rhodium and the potassium metal that links to each other with ionic linkage with pyridine carboxylic acid, two kinds of metals are by synergy, not only make the active centre rhodium obtain activation, promoted carrying out fast of reaction, and the coordination of metal rhodium is more tended towards stability, reduce sedimentary generation.
4,, make this Primary Catalysts not only can the catalysis methanol carbonyl turn to acetate and methyl acetate obtains higher yield, but also can turn to acetic anhydride by highly active catalysis acetate carbonyl because the singularity of Primary Catalysts structure of the present invention.
5, because the high activity of Primary Catalysts of the present invention and stable, make methanol carbonylation and acetate carbonyl reaction all can under lower temperature and pressure, carry out, and need not to add the hydroiodic acid HI equal solvent in addition, greatly reduce corrodibility to the reaction material.
Catalyst system of the present invention is used for catalysis methanol carbonylation reaction system acetate and acetate carbonyl reaction system acetic anhydride in polar solvent.
The present invention's employed polar solvent in reaction system is meant acetate, acetic anhydride, water or methyl acetate etc.
Catalyst system of the present invention is used for the catalysis methanol carbonylation and prepares acetate: add methyl alcohol, methyl iodide and Primary Catalysts in reaction unit respectively, their mol ratio is 1: 0.1～0.5: 0.001～0.0001, add with the methyl alcohol mol ratio be additives such as 0.001～1 lithium iodide, potassiumiodide lithium acetate, also can add with the methyl alcohol mol ratio be 0.1～1: 1 acetate, acetic anhydride, water, methyl acetate etc., charge into carbon monoxide behind the thorough mixing, temperature of reaction is 120～220 ℃, reaction pressure 20～50kg/cm
2, the reaction times is 0.5～5 hour.Reaction conditions is very gentle, only uses the promotor methyl iodide and need not to add hydroiodic acid HI.
Catalyst system of the present invention is used for the catalysis acetate carbonylization and prepares acetic anhydride: methyl acetate, methyl iodide and Primary Catalysts are joined in the reactor, their mol ratio is 1: 0.1～0.5: 0.001～0.0001, add with the methyl alcohol mol ratio be additives such as 0.001～1 lithium iodide or potassiumiodide, also can add with the methyl acetate mol ratio be 0.1～1: 1 acetate, acetic anhydride etc., charge into carbon monoxide after mixing, temperature of reaction is 120～220 ℃, reaction pressure 20～50kg/cm
2, the reaction times is 0.5～5 hour.A large amount of experimental datas show that this catalyst system has advantages of high catalytic activity to the generation of acetic anhydride.
Embodiment
Give further detailed explanation below by embodiment to technology of the present invention.
Embodiment 1
Take by weighing the pyridine-2-formic acid and the water potassium hydroxide that are 0.02 mole and be dissolved in the methyl alcohol, methyl alcohol is 0.5mol, under agitation reacts 1 hour, obtains pyridine-2-potassium formiate with excessive ether sedimentation, filtration, washing, drying.
In the methyl alcohol of the 0.5mol that contains 0.02mol pyridine-2-potassium formiate, be added dropwise to the methanol solution that contains 0.02 mole of acetic acid rhodium, wherein methyl alcohol is 0.7mol, after dropwising, continue to stir 20 minutes, and with excessive ether sedimentation, filter, be dried to constant weight, obtained bimetallic catalyst.
Embodiment 2
Take by weighing the pyridine-3-acetate and the water potassium hydroxide that are 0.01mol, be dissolved in the 0.4mol methyl alcohol, under agitation reacted 1 hour, obtain pyridine-3-potassium acetate with excessive ether sedimentation, filtration, washing, drying.
In the methyl alcohol of the 0.2mol that contains 0.01mol pyridine-3-potassium acetate, be added dropwise to the aqueous solution that contains the 0.01mol rhodium nitrate, wherein water is 0.8mol, after dropwising, continue to stir 20 minutes, and with excessive ether sedimentation, filter, be dried to constant weight, obtained bimetallic catalyst.
Embodiment 3
Take by weighing the pyridine-3-propionic acid and the water potassium hydroxide that are 0.025mol and be dissolved in the 0.8mol methyl alcohol, under agitation reacted 1 hour, obtain pyridine-3-potassium propionate with excessive ether sedimentation, filtration, washing, drying.
In the methyl alcohol of the 0.2mol that contains 0.025mol pyridine-3-potassium acetate, be added dropwise to the methanol solution that contains 0.025mol acetic acid rhodium, wherein water is 1mol, after dropwising, continue to stir 20 minutes, use excessive ether sedimentation, filter, be dried to constant weight, obtain bimetallic catalyst.
Embodiment 4
In the 250ml reactor, add the catalyzer 0.3g among the embodiment 1, methyl alcohol 2.5mol, methyl iodide 0.4mol, with air in the CO displacement still, keeping temperature of reaction is 160 ℃, CO constant voltage 33kg/cm
2, 450 rev/mins of stirring velocitys were reacted methanol conversion 95.6%, methyl acetate yield 17.8%, acetic acid yield 56.5% 2 hours.
Embodiment 5
In the 250ml reactor, add the catalyzer 0.25g of embodiment 1, methyl acetate 1.2mol, methyl iodide 0.35mol, potassiumiodide 0.015mol, behind air in the CO displacement still, keeping temperature of reaction is 185 ℃, CO constant voltage 33kg/cm
2, 500 rev/mins of stirring velocitys were reacted after 1.5 hours, and the methyl acetate transformation efficiency is 79.3%, acetate increment 13.2%, acetic anhydride yield 35.2%.
Embodiment 6
In the 250ml reactor, add the catalyzer 0.2g among the embodiment 2, methyl alcohol 2.2mol, acetate 0.3mol, methyl iodide 0.4mol, lithium acetate 0.03mol, with air in the CO displacement still, keeping temperature of reaction is 170 ℃, CO constant voltage 32kg/cm
2, 500 rev/mins of stirring velocitys were reacted after 1.5 hours, methanol conversion 99.2%, and methyl acetate yield 7.6%, acetate increment are 42.8%.
Embodiment 7
In the 250ml reactor, add the catalyzer 0.4g of embodiment 2, methyl acetate 1.5mol, acetic anhydride 0.4mol, methyl iodide 0.45mol, with air in the CO displacement still, keeping temperature of reaction is 185 ℃, CO constant voltage 32kg/cm
2, 500 rev/mins of stirring velocitys were reacted after 1.5 hours, and the methyl acetate transformation efficiency is 80.6%, acetic acid yield 9.7%, acetic anhydride gaining rate 31.7%.
Embodiment 8
In the 250ml reactor, add the catalyzer 0.7g among the embodiment 3, methyl alcohol 3mol, methyl iodide 0.38mol, lithium iodide 0.07mol, with air in the CO displacement still, keeping temperature of reaction is 185 ℃, CO constant voltage 28kg/cm
2, 500 rev/mins of stirring velocitys were reacted methanol conversion 98.6%, methyl acetate yield 15.7%, acetic acid yield 58.7% 2 hours.
Claims (5)
1, a kind of homogeneous carbonylation reaction catalyst system that is used for is made up of Primary Catalysts, promotor and additive, and wherein the Primary Catalysts structural formula is:
In the formula: R is H; X is OCOCH
3 -Or NO
3 -, m is 2 or 3, n is 0,1 or 2; Promotor is a methyl iodide; Additive is lithium iodide, potassiumiodide or lithium acetate.
2, a kind of preparation method of Primary Catalysts in the catalyst system according to claim 1, its key step is:
A) preparation organo-metallic potassium part
One water potassium hydroxide of the pyridine carboxylic acid of 1 molar part and 1～10 molar part is dissolved in the methyl alcohol or the aqueous solution of 10～100 molar part, under agitation reacted 10～60 minutes, with excessive ether sedimentation, filtration, washing, dryly must have N and O atom metal potassium organic ligand, this ligand structure is as follows:
R is H in the formula, and n is 0,1 or 2;
B) preparation rhodium-potassium bimetal complexes
The organo-metallic potassium part of 1 molar part is dissolved in the water or methanol solution of 10～100 molar part, be dissolved with the solution of 0.01～1 molar part rhodium 0～50 ℃ of dropping, isothermal reaction 10～120 minutes, ether washing, filtration, drying with excessive obtain bimetallic catalyst.
3, preparation method as claimed in claim 2 is characterized in that, described pyridine carboxylic acid is pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, pyridine-2-acetate, pyridine-3-acetate, pyridine-4-acetate or pyridine-3-propionic acid.
4, preparation method as claimed in claim 2 is characterized in that, the solution of described rhodium is the water or the methanol solution of rhodium acetate or rhodium nitrate, and the mol ratio of water or methyl alcohol and rhodium acetate or rhodium nitrate is 50～200: 1.
5, the application of catalyst system as claimed in claim 1 in methanol carbonylation system acetate and acetate carbonyl reaction system acetic anhydride.
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| CN 03102770 CN1212197C (en) | 2003-01-17 | 2003-01-17 | Catalytic system used for homogeneous hydroxylation reaction and its manufacturing method and application |
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| CN1212197C true CN1212197C (en) | 2005-07-27 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100337750C (en) * | 2004-09-24 | 2007-09-19 | 中国科学院化学研究所 | Catalyst system for carbonylation of methanol for synthesizing ethanol, and application |
| CN100372608C (en) * | 2004-11-22 | 2008-03-05 | 中国科学院化学研究所 | Catalyst system of catalytic methylester acetate or methylether synthetic acetoanhy dride and use thereof |
| CN100443173C (en) * | 2004-11-22 | 2008-12-17 | 中国科学院化学研究所 | Catalyst system for synthetizing acetic acid from methanol or synthetizing ethylanhydride from methyl acetate and use thereof |
| CN1978055B (en) * | 2005-12-08 | 2010-05-05 | 中国科学院化学研究所 | Hydroformylation catalytic system and use |
| CN100569788C (en) * | 2007-06-11 | 2009-12-16 | 江苏索普（集团）有限公司 | Rhodium acetic anhydride complex and preparation method thereof and application |
| CN101393433B (en) * | 2007-09-21 | 2011-08-03 | 浙江天成座椅有限公司 | System for monitoring and controlling amenity and safety of automobile chair and method thereof |
| CN102218343A (en) * | 2011-06-09 | 2011-10-19 | 中国科学院化学研究所 | Lithium pyridine carboxylate-rhodium acetate complex catalyst for synthesizing acetic acid and acetic anhydride through carbonylation, and preparation method and application thereof |
| US9387469B2 (en) * | 2013-12-30 | 2016-07-12 | Eastman Chemical Company | Carbonylation catalyst and process using same |
| CN109092359A (en) * | 2018-09-25 | 2018-12-28 | 煜格（北京）科技有限公司 | Catalyst system and its application of a kind of methanol carbonyl synthesized acetic acid and methyl acetate |
| CN111558395B (en) * | 2020-04-27 | 2023-09-08 | 江苏索普化工股份有限公司 | Bimetallic catalyst for methanol carbonylation reaction, and preparation method and application thereof |
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