CN1087661C - Catalyst system for preparing acetate and acetic anhydride by carbonylation and its preparing process - Google Patents
Catalyst system for preparing acetate and acetic anhydride by carbonylation and its preparing process Download PDFInfo
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- CN1087661C CN1087661C CN 97104497 CN97104497A CN1087661C CN 1087661 C CN1087661 C CN 1087661C CN 97104497 CN97104497 CN 97104497 CN 97104497 A CN97104497 A CN 97104497A CN 1087661 C CN1087661 C CN 1087661C
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Abstract
The present invention relates to a catalyst system for preparing acetic acid and acetic anhydride through carbonylation, which is composed of two main components, one of the main component is a chelate type coordination compound formed by rhodium and an organic ligand or a high molecular polymer containing oxygen, sulfur, phosphine and nitrogen. The catalyst is used for synthesizing the acetic acid, methyl acetate and acetic anhydride through carbonylation under the synergistic effect of a cocatalyst and another metal active agent. The catalyst has the activity far higher than the activity of a catalyst for manufacturing the acetic acid through methanol carbonylation by a low pressure method, and has moderate reaction conditions so as to avoid the corrosion of polar solvents and the harsh limitation of flash evaporation technology in the reaction.
Description
The present invention relates to a kind of carbonylation and prepare acetate, acetic anhydride catalyst system and method for making thereof.
By methanol carbonylation to synthesize acetic acid, the synthetic acetic anhydride of methyl acetate is present acetate, important techniques route in the acetic anhydride industry, the small molecules rhodium catalyst that U.S. Monsanto Company prepares with low-pressure process homogeneous phase solution method, and adopt the bimetal component of iridium and osmium to utilize the small molecules organic compound to be part, catalyst system, but this catalyzer unstable, and reaction is lost activity gradually, existence for the active centre of keeping reactive system, need in whole system, add hydroiodic acid HI and other interpole solvent more than 85%, must use flash process in the reaction process, like this, bring difficulty not only for product and catalyst separating but also make corrosion more serious, still change recovery and this problem of regeneration techniques that needs the use catalyzer.
Patent EP 277824 (1988), carry as catalyzer with multipolymer and superpolymer ion exchange resin and to improve the separation difficulty problem, make homogeneous reaction become heterogeneous reaction, this class carrier easily with rhodium formation complexing ring structure, but this activity of such catalysts obviously descends, and be subjected to the influence of polymer degradation, rhodium comes off in Polymer Surface separation system is thickened, and makes rhodium catalyst have unstable, and rhodium runs off serious, separation difficulty, the shortcoming of solvent corrosion, up to the present industrialization not yet.
The present invention reaches rhodium and runs off seriously separation difficulty in order to overcome the unstable of above-mentioned rhodium catalyst, the shortcoming of solvent corrosion, a kind of carbonylation reaction system acetate that is used for has been proposed, the catalyst system of acetic anhydride, it has high reaction activity and high reaction stability and low-corrosiveness concurrently.
Catalyst system of the present invention can be made up of following three parts: 1). the main body catalyzer, refer to have N, P, O, the organic compound of two or more among the S and the polymer that contains the monomer polymerization of above-mentioned feature thereof are the chelating type metal complex of part, 2). metal active agent, 3). appropriate solvent.
Above-mentioned main body catalyzer is for having N, P, and O, the organic compound of two or more among the S and the polymer that contains the monomer polymerization of above-mentioned feature thereof are the chelating type metal-complexing structure of part, its structural formula is as follows:
Described ligand structure expression formula is:
Organic compound in the part refers to have following array structure; H
2N-(CH
2)
2-NH-(CH
2)
2-NH-(CH
2)
2-NH
2
High molecular polymer refers to: poly-2-vinylpyridine, poly-4-vinylpyridine, poly-2-vinylpyridine-methyl acrylate, poly-4-vinylpyridine-methyl acrylate, polyacrylonitrile, poly-2-vinylpyridine-vinyl cyanide, polyacrylonitrile-vinyl acetate, poly-2-vinylpyridine-crotonic aldehyde, poly-2-vinylpyridine-methylene acetone, poly-4-vinylpyridine methylene acetone, poly-2-vinylpyridine-vinyl acetate, gather 2-vinylpyridine-vinyl acetate and corresponding quaternary ammonium salt or adopt above-mentioned monomer to utilize the vinylformic acid diethylene glycol dilaurate, divinylbenzene carries out crosslinked and the sub-bead that secures satisfactory grades.
A → M in the formula, B → M are of the same race or two kinds of different coordinating groups.
A, B, C, D represent Gong the coordinate N that exists in the organic group respectively, P, O, S element, four kinds of elements can be identical also can be incomplete same.
R
1-A, R
2-B, R
3-C, R
4-D, between key be singly-bound, two keys or triple bond can be mercaptan, thiophenol, thioether, aldehyde, ester, ketone and carboxylic acid derivative thereof, pyridine, imidazoles, amine, nitrile and contain the phosphine organism; R
1, R
2, R
7, R
8, be alkyl or aryl and derivative R thereof
1, R
2, R
7, R
8, four kinds of structures can be identical also can be incomplete same.
R
5, R
6Be H ,-CH
3,-OCH
3,-OH ,-COOH waits organic group.
R
3, R
4, represent the coordination organic group of coordination metal respectively, for-Cl ,-I, CO, CH
3COO-etc.
N in the formula, m＜10 refer generally to organic coordination compound; N, m＞100 refer to contain the title complex of the unit homopolymerization of said structure and linear or crosslinked bead that copolymerization forms and metal formation.
Said structure has formation 4-14 unit chelate ring (I) cationic structural between metal and the part, simultaneously, has the empty coordination structure that can form 4-13 unit ring with metal at the ortho position of this chelate structure.
Described M is the coordination metal, refers to Rh, Ir, and Ni, Co, Pd, Ru, their precursor refers to RhCl
3.3H
2O, [Rh (CO)
2X]
2(X=I, Br, Cl), IrCl
3.H
2O, NiCl
2, Ni (CH
3COO)
2, NiCO
3, CoCl
2, PdCl
2, RuCl
3.nH
2O.
X
-Be BPh
4 -, CH
3COO
-, HCO
3 -, SCN
-, CN
-, CL
-, BF
6 -The precursor of its negative ion is called precipitation agent and is respectively above-mentioned potassium, sodium, lithium, ammonium salt.Described metal active agent is meant the second kind of metal component that exists in the catalyst system, and they are IIIB, IB, VB, VIB, IA, IIA and rare earth compound.This second component metals ion or form bimetallic catalyst or be present in the reaction solution with the form of ion pair state with additive with empty ligand generation complex reaction in the described part.These promoting agents refer to LiI, LiCl, LiOAc, LiCO
3, MgSO
4, CrCl
2.H
2O, CuCl, CuCl
2, CuSO
4Cu (CH
3COO)
2, CuCO
3, LiVO
3, NaVO
3, NH
4MoO
4, CeSO
4, Ce (CH
3COO)
2, CeO, LaCl
2.H
2O, La
2O
3, Nd
2O
3, Gd
2O
3, LaNO
3.
Exist appropriate solvent to be meant that it is methyl acetate that other mixed solvent except that reaction raw materials is the carbonylation of methanol product in the described reaction system, acetate, water, reaction system need not to add other as water isopolarity solvent.
This main body catalyzer is synthetic and using method is as follows:
To contain N, P, S, the part of O element is dissolved in acetone or the methyl alcohol, (1 mole part is dissolved in the acetone of 1-100 mole, in the methyl alcohol), and at-10 ℃--40 ℃ of droppings are dissolved with RhCl
3.3H
2O, [Rh (CO)
2X]
2(X=I, Br, Cl), IrCl
3.H
2O, NiCl
2,, Ni (CH
3COO)
2, NiCO
3, CoCl
2, PdCl
2, RuCl
3.nH
2O, wherein, methyl alcohol is 50-100 with the ratio of metal: 1, (mol ratio), the ratio of part and base metal compound is 0.01-2: 1 (mol ratio) after dropwising, isothermal reaction 15-120 minute, will be dissolved with the BPh of 2-15% (mol ratio) again
4 -, CH
3COO
-, HCO
3 -, SCN
-, CN
-, Cl
-, BF
6 -The aqueous solution drip wherein, in 0 ℃ of-40 ℃ of backflow, treat the product post precipitation, place reduced pressure at room temperature to constant weight with 0 ℃ water and ether repetitive scrubbing.
This catalyzed reaction is as follows:
Methyl alcohol (methyl acetate) and methyl iodide are pressed 3: 1-8: add after the mixed of 1 (volume ratio) in the reactor, with the main body catalyzer, metal active agent (0-3 kind) adds in the reactor successively, and the ratio of the metal content of metal in the main body catalyzer and metal active agent is 1: 0-10; Add the appropriate solvent methyl acetate then, acetate, their ratio is 1: 1-3 accounts for the 0-20% (volume ratio) of whole catalyst system; Charging into carbon monoxide to gauge pressure is 10-30MPa, washs three times, then, charge into carbon monoxide: hydrogen (100: reaction gas 10-0), under gentle relatively condition (120 ℃-160 ℃, 2.5MPa-8.6MPa), carry out the synthetic acetate of carbonylation, methyl acetate, the reaction of acetic anhydride.React after half hour, most of methyl alcohol and methyl acetate all are converted into acetate, methyl acetate, acetic anhydride.Its transformation efficiency has reached 85%, and the concentration of methyl iodide remains constantly in entire reaction, finds no by product such as other impurity in the reaction and produces, and its selectivity is＞98%.
Catalyzer of the present invention has following feature:
1). the core of above-mentioned described catalyst system is to contain N, P, O, the main body catalyzer of S.Owing to contain two or more strong and weak different coordination electron donor in the part, in catalyst metal coordination thing, exist strong and weak two kinds of coordinate bonds like this, the donor atom of strong coordination ability links to each other by having certain carbochain around property with the acceptor atom of weak coordination ability, has formed the title complex that has the square plane of strong and weak metal-complexing key simultaneously.
2). because in this metal complexes, chelate structure is unsymmetric structure in the chelate structure (and strong coordination and weak coordination exist simultaneously) particularly, makes it must have good thermostability; Simultaneously, because the existence of weak donor coordination element then is easy to disassociation when the reaction addition, and the acting in conjunction of the positively charged ion of chelate ring and formation and coordination anion, carbon monoxide is easy to after cancellation and weak acceptor atom relocation bit, thereby this class catalyzer has just had strong chemical stability.
3) chelate structure that forms of above-mentioned catalyzer be unsymmetric structure wherein the existence of weak coordinate bond be the high highly active basic place of this catalyst series, make in the methyl iodide addition process, this key is easy to fracture, form the middle active body of pentacoordinate, when the adduct cancellation, the weak coordination bond of this structure recovers immediately.
4). said structure is generally positive monovalent cation structure, exist a large amount of coordinate acceptor atoms that have neither part nor lot in, this empty coordinate exists makes the performance of this catalyst series be greatly improved 1). the existence of coordinate ligand does not make this class catalyzer have certain poison resistance as yet.2). use this class catalyzer because it exists chelate structure and adjacent basic empty coordination; its carbon monoxide in reaction process is protected under the insufficient condition; adjacent base can participate in sloughing the small molecules of metal-complexing; form the chelating body of three teeth and four tooth coordination structures; improved the stability of this catalyzer greatly; solved the weakness of micromolecule catalyst in the past; the direct advantage of these catalyzer characteristics is to use in the industry has avoided complicated flash process; can adopt general distillating method to get final product; need not to increase the polarizable medium that resembles hydroiodic acid HI and so in the catalyst system; requirement and capital investment to material all reduce greatly; the recovery of catalyzer and regenerating unit be all corresponding to have obtained basic simplification .3). above-mentioned not coordinate ligand acceptor atom; easily and methyl iodide generate corresponding quaternary ammonium salt and sulfonium salt, thereby the making full use of and increase mass transfer process in the reaction system of the promotor methyl iodide that is highly advantageous to.
5). the said structure catalyzer can be stated from inorganic and the polymer matrix, and described polymer matrix is the polymer matrix of grafted or copolymerization and modification.
6). another characteristics of this catalyst system have been to use the higher metal additive of content, make that the precious metal composition significantly reduces in its catalyzer, can be reduced to 30% of micromolecule catalyst, and under the constant situation of its reaction preference, its reactive behavior can rise to its 1-1.5 doubly greatly, the introducing of second kind of metal has improved the toxin immunity of its catalyzer on the one hand greatly, has also further improved the yield of catalyst stability and reaction final product on the other hand.
7). the reaction conditions of the employed catalyzer of this catalyzer is extremely gentle, and reaction system need not to add polarizable medium such as hydroiodic acid HI, only add as methyl acetate, acetate, methyl alcohol is several as solvent.
The present invention has following positive effect:
1). high speed of response and highly selective
Can in the dividing potential drop of carbon monoxide 40kg/cm
2Under 100 ℃ temperature condition, the carbonylation reaction that carries out.At 140 ℃, methanol conversion speed can reach 1200gAcOH/gRh.h, and by the methyl alcohol that has transformed, its acetate production rate can reach 80-90%, never finds the by product as dme in reaction process, and the selectivity of its carbonylation reaction is 99%.
2). heat-resisting and chemical-resistant stability
The catalytic activity of catalyzer of the present invention increases along with the increase of temperature of reaction, still there is not tangible downtrending when reaching 190 ℃, and under such use temperature condition, other homogeneous phase micromolecule catalyst often makes active specy decompose and causes reactive behavior to descend, from the research of thermogravimetric curve, catalyzer of the present invention just begins weightlessness under 230 ℃ condition.
3) Wen He reaction conditions and low-corrosiveness
Temperature of reaction is 100 ℃-190 ℃, and the gauge pressure of reactive system is 12-60kg/cm
2Stirring velocity is greater than 170 rev/mins, add methyl alcohol and methyl iodide in the system, catalyzer and metal additive and appropriate solvent, methanol conversion can meet and exceed the level of Meng Shandou, the content of methyl iodide remains unchanged substantially in the reaction system, simultaneously, reactive system is simple, need not to add as hydroiodic acid HI isopolarity medium, alleviated the corrosion of reaction medium greatly to reaction unit, and, in reactive system because the catalysis thermostability and the chemical stability of the excellence of catalyzer, this catalyst system need not to use complicated flash process, and adopt common distil process to get final product, and simplified all separate complex in the technology of Meng Shan in the past so greatly, corrodibility reaches the big shortcoming of facility investment greatly.
The feature of its obvious catalyzer is as shown in the table:
| Catalyzer | Example 2 | Example 6 | Example 9 | Example 10 | Example 11 | Example 17 | Example 18 | Example 19 | Example 20 | Example 21 | Example 22 |
| Active gAcO H/gR h.h | 843 | 756 | 673 | 1032 | 998 | 732 | 1276 | 936 | 1435 | 1153 | 1893 |
| Reaction conditions | T： 135℃ P： 4.0Mp a | T： 135℃ P： 4.0Mp a | T： 165℃ P： 5.0Mp a | T： 135℃ P： 4.0Mp a | T： 135℃ P： 3.0Mp a | T： 135℃ P： 3.0Mp a | T： 135℃ P： 4.0Mp a | T： 135℃ P： 3.0Mp a | T： 135℃ P： 4.0Mp a | T： 135℃ P： 4.0Mp a | T： 135℃ P： 4.0Mp a |
| Selectivity | ＞99％ | ＞99％ | ＞90％ | ＞97％ | ＞98％ | ＞95％ | ＞98％ | ＞99％ | ＞99％ | ＞99％ | ＞99％ |
| Medium | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol |
| Product | The acetate acetic anhydride | Acetate | Acetate | Acetate | Acetate | Acetate | Acetate | Acetate | Acetate | Acetate | Acetate |
| Separation condition | Common distillation | Common distillation | Common distillation | Common distillation | Common distillation | Common distillation | Common distillation | Common distillation | Common distillation | Common distillation | Common distillation |
| Stability | The 1000h non-inactivation | The 1000h non-inactivation | No RhI 3Generate | No RhI 3Generate | No RhI 3Generate | No RhI 3Generate | No RhI 3Generate | No RhI 3Generate | No RhI 3Generate | No RhI 3Generate | No RhI 3Generate |
Embodiment 1:
Get poly-2-vinylpyridine (poly-4-vinylpyridine, or polyacrylonitrile) homopolymer 10g, be dissolved in the 50ml acetone, will be dissolved in 1.5g in the methyl alcohol of 20ml, Rh
2(CO)
4Cl
2Drip in above-mentioned solution, be heated to 40 ℃, magnetic agitation dripped the aqueous solution of sodium tetraphenylborate after 1 hour, and post precipitation obtains the lemon yellow carbonylic rhodium compound.
Embodiment 2:
Get poly-2-vinylpyridine-methyl acrylate copolymer 1.0g, be dissolved in the 7.0ml acetone, to be dissolved in 0.02g in the methyl alcohol of 20ml, dichloro four carbonyl diurethane rhodiums drip in above-mentioned solution, be heated to 40 ℃, after the magnetic agitation 1 hour, drip the aqueous solution of sodium borohydride, post precipitation can obtain the carbonylic rhodium compound with chelate structure of lemon yellow.Get the above-mentioned title complex of doing, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its rhodium content be 0.00004 mole of rhodium/liter, the gauge pressure 4.0Mpa. of the carbon monoxide of reaction heats up 135 ℃ and reacted 2 hours, methanol conversion is 90%, acetate productive rate 40%, methyl acetate transformation efficiency 30%.Continue 2 hours afterreaction systems of reaction and begin to have occurred acetic anhydride, react after 5 hours, methanol conversion is 100%, and acetic acid yield is 45%, and the acetic anhydride yield is 23%, and catalysis speed is 843gAcOH/gRh.h.Its catalytic activity did not demonstrate any reduction after this catalyzer moved 1000 hours continuously.
Embodiment 3:
Get poly-4-vinylpyridine-methyl acrylate copolymer 1.0g, be dissolved in the 5.0ml acetone, will be dissolved in 0.05g in the methyl alcohol of 20ml, Rh
2(CO)
4Cl
2Drip in above-mentioned solution, be heated to 40 ℃, magnetic agitation dripped the aqueous solution of sodium tetraphenylborate after 1 hour, and post precipitation obtains the carbonylic rhodium compound of lemon yellow chelate structure.
Embodiment 4:
Get poly-4-vinylpyridine-acrylonitrile copolymer 1.0g, be dissolved in the 5.0ml acetone, will be dissolved in 0.05g in the methyl alcohol of 20ml, Rh
2(CO)
4Cl
2Drip in above-mentioned solution, be heated to 40 ℃, magnetic agitation dripped the aqueous solution of sodium tetraphenylborate after 1 hour, and post precipitation can obtain the carbonylic rhodium compound of lemon yellow chelate structure.
Embodiment 5:
Get poly-2-vinylpyridine-vinyl acetate copolymer 1.0g, be dissolved in the 5.0ml acetone, to be dissolved in 0.05g in the methyl alcohol of 20ml, nickel acetate drips in above-mentioned solution, be heated to 40 ℃, feed CO (carbon monoxide converter) gas (normal pressure), magnetic agitation is after 26 hours, drip the aqueous solution of sodium tetraphenylborate, post precipitation obtains nickel complex.
Embodiment 6:
Get poly-4-vinylpyridine-methyl acrylate copolymer 1.0g, be dissolved in the 5.0ml acetone, to be dissolved in 0.05g in the methyl alcohol of 20ml, iridous chloride drips in above-mentioned solution, feed under the condition of carbon monoxide, be heated to 40 ℃, after the magnetic agitation 1 hour, drip the aqueous solution of sodium tetraphenylborate, post precipitation can obtain the above-mentioned title complex of doing of the complex of iridium with chelate structure of lemon yellow, adds in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its iridium content be 0.00005 mole of rhodium/liter, the gauge pressure 4.0MPa of the carbon monoxide of reaction, the 135 ℃ of reactions 2 hours that heat up, methanol conversion is 90%, acetate productive rate 40%, catalysis speed are 756gAcOH/gRh.h.Its catalytic activity did not demonstrate any reduction after this catalyzer moved 1000 hours continuously.
Embodiment 7:
Get poly-4-vinylpyridine (or 2-vinylpyridine)-methylene acetone copolymer 1 .0g, be dissolved in the 5.0ml acetone, will be dissolved in 0.05g in the methyl alcohol of 20ml, Rh
2(CO)
4Cl
2Drip in above-mentioned solution, be heated to 40 ℃, magnetic agitation dripped the aqueous solution of sodium bicarbonate sodium after 1 hour, and post precipitation obtains the lemon yellow carbonylic rhodium compound.
Embodiment 8:
Get poly-4-vinylpyridine (or 2-vinylpyridine)-crotonic aldehyde copolymer 1 .0g, be dissolved in the 5.0ml acetone, will be dissolved in 0.05g in the methyl alcohol of 20ml, Rh
2(CO)
4Cl
2Drip in above-mentioned solution, be heated to 40 ℃, magnetic agitation dripped the aqueous solution of lithium acetate after 1 hour, and post precipitation can obtain the carbonylic rhodium compound of chelate structure.
Embodiment 9:
Get poly-4-vinylpyridine-methyl acrylate copolymer 1.0g, be dissolved in the 5.0ml acetone, to be dissolved in 0.05g in the methyl alcohol of 20ml, nickelous chloride drips in above-mentioned solution, feed under the condition of carbon monoxide, be heated to 40 ℃, magnetic agitation is after 30 hours, drip the aqueous solution of yellow soda ash, post precipitation can obtain the nickel complex with chelate structure of little green; Get the above-mentioned title complex of doing, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its nickel content be 0.00009 mole of rhodium/liter, add Neodymium trioxide, the mol ratio that makes Ni/Nd is 1.2, the gauge pressure 5.0Mpa of the carbon monoxide of reaction, the 165 ℃ of reactions 2 hours that heat up, methanol conversion is 90%, acetate productive rate 40%, methyl acetate transformation efficiency 30%.Catalysis speed is 673gAcOH/gRh.h.
Embodiment 10:
Get poly-4-vinylpyridine (2-vinylpyridine)-methyl acrylate (or methylene acetone) and, be dissolved in the 5.0ml acetone, will be dissolved in 0.05g in the methyl alcohol of 20ml, Rh with the crosslinked bead of divinylbenzene (or vinylformic acid diethylene glycol dilaurate) (degree of crosslinking is 5%) 1.0g
2(CO)
4Cl
2Drip in above-mentioned solution, be heated to 40 ℃, magnetic agitation dripped the aqueous solution of Sodium Thiocyanate 99 after 1 hour, and post precipitation can obtain the carbonylic rhodium compound with chelate structure of lemon yellow; Get the above-mentioned title complex of doing, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its rhodium content be 0.00004 mole of rhodium/liter, interpolation LaCl
2.H
2O, La
2O
3Or LaNO
3The mol ratio that makes Rh/La is 1.2, the gauge pressure 4.0Mpa of the carbon monoxide of reaction, and the 135 ℃ of reactions 2 hours that heat up, methanol conversion is 90%, acetate productive rate 40%, methyl acetate transformation efficiency 30%.Catalysis speed is 1032gAcOH/gRh.h.
Embodiment 11:
Get poly-4-vinylpyridine (or 2-vinylpyridine)-methylene acetone copolymer 1 .0g, be dissolved in the 5.0ml acetone, to be dissolved in that the 0.03g Trichlororhodium drips in above-mentioned solution in the methyl alcohol of 20ml, be heated to 40 ℃, feed under the condition of carbon monoxide, after the magnetic agitation 1 hour, drip the aqueous solution of sodium iodide, what post precipitation can obtain lemon yellow has a chelate structure rhodium complex; Get the above-mentioned title complex of doing, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its rhodium content be 0.00004 mole of rhodium/liter, interpolation Gl
2O
3, the mol ratio that makes Rh/Gl is 1.5, the mixed solvent of the methyl acetate of reaction system interpolation 10% and 5% acetate, and the gauge pressure 3.0Mpa of the carbon monoxide of reaction, the 135 ℃ of reactions 2 hours that heat up, methanol conversion is 95%, catalysis speed is 998gAcOH/gRh.h.
Embodiment 12:
Get poly-4-vinylpyridine (or 2-vinylpyridine)-methylene acetone copolymer 1 .0g, be dissolved in the 5.0ml acetone, to be dissolved in 0.05g in the methyl alcohol of 20ml, ruthenium trichloride drips the mixture that feeds carbon monoxide and hydrogen in above-mentioned solution, be heated to 40 ℃, after the magnetic agitation 14 hours, drip the aqueous solution of sodium tetraphenylborate, post precipitation can obtain bolarious ruthenium title complex with chelate structure.
Embodiment 13:
Get part
1g is dissolved in the 10ml acetone, under the condition of magnetic agitation, make it to dissolve fully or, add 2gRh
2(CO)
4I
2, under keeping 20 ℃, the back behind the stirring 30min, drips 2% KI solution 3ml, produce precipitation process post precipitation process washing and filtering thereupon, and drying can obtain reddish-brown chelate structure title complex.
Embodiment 14:
Get H
2N-(CH
2)
2-NH-(CH
2)
2-NH-(CH
2)
2-NH
2Part 3g is dissolved in the acetone, adds 1g RhCl
3After, feed pure carbon monoxide, 30 ℃ were refluxed 23 hours under the condition of magnetic agitation, dripped the aqueous solution 4ml of 4% sodium tetraphenylborate, after question response finishes, through the ether washing, dry with getting final product to such an extent that reddish-brown has the chelating type structural coordination compound.
Embodiment 15: get
Part 5g is dissolved in the acetone, adds 2gRh
2(CO)
4I
2, methanol solution, feed pure carbon monoxide, under the condition of magnetic agitation, 30 ℃ were refluxed 2 hours, dripped the aqueous solution of 2% sodium tetraphenylborate, produced post precipitation immediately through washing, drying can obtain faint yellow title complex with chelate structure.
Embodiment 16 gets
Part 5g is dissolved in the acetone, adds 2g Rh
2(CO)
4I
2, methanol solution, feed pure carbon monoxide, under the condition of magnetic agitation, 30 ℃ were refluxed 2 hours, dripped the aqueous solution of 2% sodium tetraphenylborate, produced post precipitation immediately through washing, drying can obtain the title complex of faint yellow chelate structure.
Embodiment 17:
Get title complex among the embodiment 18, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its rhodium content be 0.00004 mole of rhodium/liter, the gauge pressure 4.0Mpa of carbon monoxide, the 135 ℃ of reactions 2 hours that heat up, methanol conversion is 85%, acetate productive rate 40%, methyl acetate transformation efficiency 30%.Catalysis speed is 723gAcOH/gRh.h.
Embodiment 18:
Get the title complex of being done among the embodiment 17, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its rhodium content be 0.00004 mole of rhodium/liter, interpolation, CeSO
4Or Ce (CH
3COO)
2The mol ratio that makes Rh/Ce is 1.2, the gauge pressure 4.0Mpa of the carbon monoxide of reaction.Heat up 135 ℃ and reacted 2 hours, methanol conversion is 90%, acetate productive rate 40%, methyl acetate transformation efficiency 30%.Catalysis speed is 1276gAcOH/gRh.h.
Embodiment 19:
Get poly-4-vinylpyridine (or 2-vinylpyridine)-methylene acetone copolymer 1 .0g, be dissolved in the 5.0ml acetone, to be dissolved in that the 0.03g Trichlororhodium drips in above-mentioned solution in the methyl alcohol of 20ml, be heated to 40 ℃, feed under the condition of carbon monoxide, after the magnetic agitation 1 hour, drip the aqueous solution of sodium iodide, what post precipitation can obtain lemon yellow has a chelate structure rhodium complex; Get the above-mentioned title complex of doing, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its rhodium content be 0.00004 mole of rhodium/liter, interpolation CuCl, CuCl
2, CuSO
4Cu (CH
3COO)
2Or CuCO
3, the mol ratio that makes Rh/Cu is 1.5, the mixed solvent of the methyl acetate of reaction system interpolation 10% and 5% acetate, and the gauge pressure 3.0Mpa of the carbon monoxide of reaction, the 135 ℃ of reactions 2 hours that heat up, methanol conversion is 99%, catalysis speed is 936gAcOH/gRh.h.
Embodiment 20:
Get the title complex of being done among the embodiment 7, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its rhodium content be 0.00004 mole of rhodium/liter, interpolation, LiVO
3NaVO
3, the mol ratio that makes Rh/V is 1.2, the gauge pressure 4.0Mpa of the carbon monoxide of reaction.Heat up 135 ℃ and reacted 2 hours, methanol conversion is 96%, acetate productive rate 46%, methyl acetate transformation efficiency 26%.Catalysis speed is 1435gAcOH/gRh.h.
Embodiment 21:
Get the title complex of being done among the embodiment 8, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its rhodium content be 0.00004 mole of rhodium/liter, interpolation NH
4MoO
43, the mol ratio that makes Rh/Mo is 1.2, the gauge pressure 4.0Mpa of the carbon monoxide of reaction.Heat up 135 ℃ and reacted 2 hours, methanol conversion is 94%, acetate productive rate 42%, and methyl acetate transformation efficiency 29%, catalysis speed is 1153gAcOH/gRh.h.
Embodiment 22:
Get the title complex of being done among the embodiment 7, add in the autoclave, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio is 6.5: 1), its rhodium content be 0.00004 mole of rhodium/liter, interpolation CrCl
2.H
2O, the mol ratio that makes Rh/Cr is 1.2, the gauge pressure 4.0Mpa of the carbon monoxide of reaction, the 135 ℃ of reactions 2 hours that heat up, methanol conversion is 96%, catalysis speed is 1083gAcOH/gRh.h.
Claims (7)
1. a carbonylation prepares acetate, acetic anhydride catalyst system, it is characterized in that described catalyst system is by main body catalyzer, metal active agent and solvent composition, described main body catalyzer have among N, P, O, the S two or more organic compound and the polymer that contains the monomer polymerization of above-mentioned feature be the chelating type metal complex of part, its structure expression is as follows:
Described ligand structure expression formula is:
A, B, C, D represent Gong coordinate N, P, O, the S element that exists in the organic group respectively, four kinds of elements can be identical also can be incomplete same,
R
1, R
2, R
7, R
8Be alkyl or aryl and derivative thereof; R
1, R
2, R
7, R
8Can be identical also can be incomplete same,
R
5, R
6For H ,-CH
3,-OCH
3,-OH or-the COOH organic group,
R
3, R
4Represent the coordination organic group of coordination metal respectively, be Cl, I, CO or CH
3COO
-,
N in the formula, m＜10 or n, m＞100,
Described M is coordination metal Rh, Ir, Ni, Co, Pd or the Ru of this title complex,
Title complex has A → M in the formula, of the same race or the two kinds of different coordinate bonds of B → M form the positive monovalent cation structure of 4-14 unit's chelate ring, simultaneously between metal and the part in the structure, sting the ortho position of closing structure at this and exist the empty coordination element that can form 4-13 unit ring with metal
X
-Be BPh
4 -, CH
3COO
-, HCO
3 -, SCN
-, CN
-, Cl
-Or BF
6 -,
Described metal active agent is LiI, LiCl, LiOAc, LiCO
3, MgSO
4, CrCl
2.H
2O, CuCl, CuCl
2, CuSO
4, Cu (CH
3COO)
2, CuCO
3, LiVO
3, NaVO
3, NH
4MoO
4, CeSO
4, Ce (CH
3COO)
2, CeO, LaCl
2.H
2O, La
2O
3, Nd
2O
3, Gd
2O
3Or LaNO
3,
Described solvent be methyl acetate and acetate by 1: the mixed solvent of 1-3.
2. a kind of carbonylation according to claim 1 prepares acetate, acetic anhydride catalyst system, it is characterized in that described organic compound is the compound with following array structure:
Or
Or
Or
3. a kind of carbonylation according to claim 1 prepares acetate, the acetic anhydride catalyst system is characterized in that described high molecular polymer refers to: poly-2-vinylpyridine, poly-4-vinylpyridine, poly-2-vinylpyridine-methyl acrylate, poly-4-vinylpyridine-methyl acrylate, polyacrylonitrile, poly-2-vinylpyridine-vinyl cyanide, polyacrylonitrile-vinyl acetate, poly-2-vinylpyridine-crotonic aldehyde, poly-2-vinylpyridine-methylene acetone, poly-4-vinylpyridine-methylene acetone, gather 2-vinylpyridine-vinyl acetate or poly-4-vinylpyridine-vinyl acetate and corresponding quaternary ammonium salt or adopt above-mentioned polymer monomer to utilize linking agent vinylformic acid diethylene glycol dilaurate, divinylbenzene carries out crosslinked and obtains the high molecular polymer bead.
4. a kind of carbonylation according to claim 1 prepares acetate, the acetic anhydride catalyst system is characterized in that described coordination metal precursor refers to RhCl
3.3H
2O, [Rh (CO)
2X]
2X=I in the formula, Br, Cl, IrCl
3.H
2O, NiCl
2, Ni (CH
3COO)
2, NiCO
3, CoCl
2, PdCl
2Or RuCl
3.nH
2The O compound.
5. a kind of carbonylation according to claim 1 prepares acetate, acetic anhydride catalyst system, it is characterized in that in the described part R
1-A, R
2-B, R
3-C, R
4Key between the-D is singly-bound, two key or triple bond, can and contain the phosphine organism for mercaptan, thiophenol, thioether, aldehyde, ester or ketone and carboxylate derivatives or pyridine, imidazoles, amine or nitrile.
6. a kind of carbonylation according to claim 1 prepares acetate, acetic anhydride catalyst system, it is characterized in that metal in the described metal active agent is present in the sky coordination or is present in the reaction solution.
7. a kind of carbonylation according to claim 1 prepares the synthetic method of acetate, acetic anhydride catalyst system, and its feature step is in the following order carried out:
(1) the main body catalyzer is synthetic: the part that will contain N, P, O, S element, be dissolved in acetone or the methyl alcohol, 1 mole part is dissolved in the freezing acetone of 1-100 mole, the methyl alcohol, stirs and feed at high speed under the condition of CO of 0.1-10MPa, is dissolved with RhCl-10 ℃ of-40 ℃ of droppings
3.3H
2O, [Rh (CO)
2X]
2X=I in the formula, Br, Cl, IrCl
3.H
2O, NiCl
2, Ni (CH
3COO)
2, NiCO
3, CoCl
2, PdCl
2Or RuCl
3.nH
2The methanol solution of O, wherein the mol ratio of methyl alcohol and metal is 50-100: 1, after dropwising, isothermal reaction 15-120 minute, will be dissolved with the BPh that mol ratio is 2-15% again
4 -, CH
3COO
-, HCO
3 -, SCN
-, CN
-, Cl
-Or BF
6 -The aqueous solution drip wherein, in 0-40 ℃ of backflow, treat the product post precipitation, water and ether repetitive scrubbing place reduced pressure at room temperature to constant weight,
(2) main body catalyzer and metal active agent are added in the reactor, with methyl alcohol or methyl acetate and methyl iodide by volume 3: 1-8: 1 mixed becomes reaction solution then to add in the reactor, and the ratio of the metal in the main body catalyzer and the metal of promoting agent is 1: 0-10; Wherein the main body catalyst consumption accounts for the long-pending 1-5% of entire reaction liquid, adds appropriate solvent methyl acetate, acetate then, and their ratio is 1: 1-3 accounts for the 5-15% of whole catalyst system by volume; Charge into carbon monoxide by volume: hydrogen 100: 10-0, at 120 ℃-160 ℃, under the gentle relatively condition of 2.5MPa-8.6MPa, finish carbonylation reaction, described metal active agent is LiI, LiCl, LiOAc, LiCO
3, MgSO
4, CrCl
2.H
2O, CuCl, CuCl
2, CuSO
4, Cu (CH
3COO)
2, CuCO
3, LiVO
3, NaVO
3, NH
4MoO
4, CeSO
4, Ce (CH
3COO)
2, CeO, LaCl
2.H
2O, La
2O
3, Nd
2O
3, Gd
2O
3Or LaNO
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104497 CN1087661C (en) | 1997-06-23 | 1997-06-23 | Catalyst system for preparing acetate and acetic anhydride by carbonylation and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104497 CN1087661C (en) | 1997-06-23 | 1997-06-23 | Catalyst system for preparing acetate and acetic anhydride by carbonylation and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1203122A CN1203122A (en) | 1998-12-30 |
| CN1087661C true CN1087661C (en) | 2002-07-17 |
Family
ID=5167406
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97104497 Expired - Fee Related CN1087661C (en) | 1997-06-23 | 1997-06-23 | Catalyst system for preparing acetate and acetic anhydride by carbonylation and its preparing process |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI272123B (en) * | 2002-12-20 | 2007-02-01 | Showa Denko Kk | Heteropolyacid and/or its salt supported catalyst, production process of the catalyst and production process of compound using the catalyst |
| 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 |
| CN102180783B (en) * | 2011-02-25 | 2013-06-12 | 昆明贵金属研究所 | Method for selectively separating rhodium (II) acetate from rhodium (II) acetate recrystallization waste liquor |
| CN103977834B (en) * | 2014-06-03 | 2016-01-27 | 江苏索普（集团）有限公司 | The preparation method of the catalyst that ethyl alcohol carbonylation is propionic acid synthesized and application |
| CN109453815B (en) * | 2017-09-06 | 2021-09-07 | 中国科学院大连化学物理研究所 | Organic phosphine-containing polymer carrier-loaded rhodium-based catalyst, and preparation and application thereof |
| CN109453812B (en) * | 2017-09-06 | 2021-09-07 | 中国科学院大连化学物理研究所 | Organic nitrogen-containing polymer carrier loaded Rh-based catalyst and preparation and application thereof |
| CN112645810B (en) * | 2020-12-17 | 2023-04-28 | 南京延长反应技术研究院有限公司 | Enhanced reaction system and method for preparing acetic acid by methanol carbonylation |
| CN112679333B (en) * | 2020-12-17 | 2023-07-21 | 南京延长反应技术研究院有限公司 | Reaction system and method for preparing acetic acid by methanol carbonylation |
| CN114515605A (en) * | 2022-02-16 | 2022-05-20 | 江苏索普（集团）有限公司 | Preparation and application of ruthenium-palladium double-active-center catalyst for synthesizing acetic acid or acetic anhydride through carbonylation |
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1997
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|---|---|
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