CN1037584C - Iminazoles-rhodium catalyst and its prepn - Google Patents
Iminazoles-rhodium catalyst and its prepn Download PDFInfo
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Abstract
The present invention relates to a high polymer rhodium catalyst formed by a high polymer containing an imidazole ring side group to bind with a rhodium activity species. Methyl halide and particularly methyl iodide are used as cocatalysts, or other auxiliary agents, such as litium salt, etc., and additives are added so as to produce acetic acid by methanol carbonylation or synthesize acetic anhydride by methyl acetate carbonylation under the reaction condition with comparatively moderate temperature and pressure. The high polymer rhodium catalyst has the characteristics of high catalytic activity, selectivity and stability in a reaction system.
Description
The invention belongs to the polymer rhodium catalyst.
Carbon monoxide is made acetate, is made acetic anhydride with the methyl acetate reaction with the methyl alcohol reaction under the effect of catalyzer, and this is the new chemical synthetic method that grows up in the 40-50 age in this century, is called oxo process.The beginning of the seventies, people such as the Paulik of Monsanto company was about the invention (U.S. Pat 3769329,1973 years) of rhodium catalyst, for new enforcement approach has been opened up in the oxo process industrialization.But this class rhodium compound becomes trivalent rhodium inactivation precipitation easily in the running use, has increased the reclaiming expense of catalyzer.In actual production process,, except that guaranteeing enough carbon monoxide pressure of tension, also adopt the way that adds big water gaging and hydrogen iodide usually, to guarantee the stability of catalyzer in order to help improving or keep catalytic activity and prevent the catalyst deactivation precipitation.But so, not only reaction medium is more serious to the corrosion phenomenon of production unit, and water content increases in the thick acetic acid that distills at first, also has water-hydroiodic acid HI azeotrope and occurs, and product separates more complicated, and energy consumption significantly rises.
People such as Drago (US4328125, nineteen eighty-two) adopt pyridines resin binding rhodium active specy as catalyzer, carry out methanol carbonylation, find the suitable of its catalytic activity and homogeneous catalyst, just temperature of reaction that is adopted and pressure condition (being respectively 120-130 ℃ and 0.4-1.1MPa) make its catalytic rate and space-time yield very low, do not have industrial using value to say.After this, 4-vinylpyridine resinoid (European patent EP 277824 appears adopting in succession, 1988), 2-vinylpyridine copolymer (Chinese patent CN1004750,1989) and vinyl pyrrolidone superpolymer (US5281359,1994) binding rhodium active specy as the report of carbonylating catalyst.Some performance of these catalyzer particularly thermostability generally makes moderate progress, then situation is different aspect other catalytic performance, for example the raising of the catalytic activity of vinyl pyrrolidone superpolymer rhodium catalyst carbonylation system acetate is more, but the space-time yield of carbonylation system acetic anhydride is not fine.
The object of the invention is, by changing the The Nomenclature Composition and Structure of Complexes of polymer rhodium catalyst, further improve the catalytic activity and the stability of catalyzer, under gentle relatively reaction conditions, realize the carbonylation method production of acetate and acetic anhydride, and cut down the consumption of energy and the reclaiming expense of catalyzer.
The invention provides the polymer rhodium catalyst that a kind of novel superpolymer part binding rhodium active specy that contains the imidazolyl side chain forms, it compared with prior art, have higher catalytic activity and stability, the comprehensive use properties of catalyzer improves significantly.
Technology of the present invention constitutes, and mainly comprise being used for the polymer rhodium catalyst that has the imidazole ring side group and method for making and the purposes that carbonylation reaction is made acetate and acetic anhydride respectively, and the reaction system that adapts is therewith formed and using method.
The polymer rhodium catalyst that is used for carbonylation reaction, it is characterized in that: the polymer rhodium catalyst is an imidazoles polymer rhodium catalyst, promptly on part superpolymer or oligomer molecules chain, have the imidazole ring side group, and binding rhodium active specy thus, the content of the reactive metal rhodium of institute's binding accounts for the 0.5-10% of total catalyst weight; Nitrogen-atoms on the imidazole ring is partly by quaternized; Part superpolymer or oligopolymer are meant the vinyl imidazole family macromolecule; The vinyl imidazole family macromolecule is meant the homopolymer of N-vinyl imidazole or by the multipolymer of divinyl benzene crosslinked.
The method for making that is used for the polymer rhodium catalyst of carbonylation reaction, it is characterized in that being divided into three steps carries out: the preparation of (1) part, promptly earlier N-divinyl imidazoles is carried out free radical at 60-90 ℃ and cause solution or suspension polymerization, obtain ethene imidazoles homopolymer; Perhaps in ethene imidazoles monomer, add the linking agent Vinylstyrene, then obtain cross-linking copolymer; (2) quaternized, be about to homopolymer or cross-linking copolymer and join in the methyl iodide, perhaps again with solvent methanol or benzene dilution, reaction backflow 0.5-24 hour, pressure reducing and steaming solvent or through filtering and washing, drying under reduced pressure obtains on the imidazole ring nitrogen-atoms part by quaternised superpolymer or oligopolymer part; (3) Preparation of Catalyst is about to above part and four carbonyl dihalo-s, two rhodiums [Rh (CO)
2X]
2(X=Cl, Br I) join in methyl alcohol or benzene or the mixed solvent by the content 0.5-10wt% of rhodium in catalyzer, under room temperature and argon shield stirring reaction 0.5-4 hour, naturally dry or the filtering solvent, drying under reduced pressure, sub-rhodium catalyst particle or crystal powder finished product secure satisfactory grades; Perhaps original position forms in reaction system, precursor compound four carbonyl dihalo-s, two rhodiums or the Trichlororhodium hydrate that are about to above-mentioned part and rhodium are the 0.1-50mmol/L scope according to the content 0.5-10wt% or the content of rhodium in reaction system of rhodium in catalyzer, directly join in the carbonylation reaction system, closed reactor, be pressed into CO, in the temperature reaction process, just form described imidazoles polymer rhodium catalyst automatically.
Be used to generate the purposes of the carbonylation reaction polymer rhodium catalyst of acetate, it is characterized in that catalyst levels is counted 0.5-50mmol/L with the content of rhodium in the reaction solution that comprises methyl alcohol and catalyzer in the carbonylation reaction system, the consumption of promotor remains on the 0.5-8mol/L scope with the densitometer in reaction solution, promotor in reaction solution content in the 1-20wt% scope, metallic lithium (Li) is 10-500 to the ratio of rhodium atom (Rh), and the solvent load by volume accounts for the 5-90% of reaction medium; The optimum content of rhodium in reaction solution is 1-20mmol/L, the optimum amount of promotor is counted 1-5mol/L with the concentration in reaction solution, the optimum content of promotor in reaction solution is 5-15wt%, metallic lithium (Li) is 60-250 to ratio the best of rhodium atom (Rh), and the scope that solvent optimum amount by volume accounts for reaction medium is 20-55%; Promotor is a methyl halide, and promotor is the metal lithium salts, and solvent is an acetate; Methyl halide is a methyl iodide; The metal lithium salts is lithium iodide or lithium acetate.
Be used to generate the purposes of the carbonylation reaction polymer rhodium catalyst of acetic anhydride, it is characterized in that catalyst levels is counted 0.5-50mmol/L with the content of rhodium in the reaction solution that comprises methyl acetate and catalyzer in the carbonylation reaction system, the consumption of promotor remains on the 0.5-8mol/L scope with the densitometer in reaction solution, promotor in reaction solution content in the 1-20wt% scope, metallic lithium (Li) is 10-500 to the ratio of rhodium atom (Rh), solvent based on methyl acetate, total concn in reaction solution is counted 3-8mol/L, and methyl acetate/acetate mol ratio is controlled at 1-10.The optimum content of rhodium in reaction solution is 1-20mmol/L, the optimum amount of promotor is counted 1-5mol/L with the concentration in reaction solution, promotor content the best in reaction solution is 5-15wt%, metallic lithium (Li) is 60-250 to ratio the best of rhodium atom (Rh), and methyl acetate/acetate mol ratio optimum control is between 3-6; Promotor is a methyl halide, and promotor is the metal lithium salts; Methyl halide is a methyl iodide, and the metal lithium salts is lithium iodide or lithium acetate.
The polymer rhodium catalyst that is used for carbonylation reaction that the present invention is developed into has the imidazole ring side group on the high-polymer molecular chain, and binding rhodium active specy thus; The macromolecule ligand that contains imidazole group, both can make the oligomer of low-molecular-weight linearity, form the homogeneous catalyst of solubility, also can make the copolymer ligand of high-crosslinking-degree, the catalyzer that forms is insoluble and swelling just becomes the heterogenize catalysts in reaction system.Such catalyzer is in carbonylation reaction system, when adding the promotor methyl iodide or adding other auxiliary agent and additive again, for example metallic salt such as lithium iodide or lithium acetate promotor and acetate, methyl acetate or acetic anhydride equal solvent, under certain temperature of reaction and pressure condition, promptly show high catalytic activity and highly selective, and stability also increases significantly.The temperature range that this catalyzer carries out carbonylation reaction is 90-210 ℃, generally in reaction more than 140 ℃, can reach catalytic rate and space-time yield with industrial application value, wherein with 150-180 ℃ temperature range best results: except that the carbonylation catalytic activity improved greatly, carbonylation of methanol was produced the selectivity of acetate and methyl acetate greater than 99%; The selectivity of acetate carbonyl production acetic anhydride is 100%.Described superpolymer be the vinyl imidazole family macromolecule, the most frequently used be the homopolymer of N-vinyl imidazole or by the multipolymer of divinyl benzene crosslinked, the nitrogen-atoms of imidazole ring side group is partly by quaternized on the macromolecular chain.
In this polymer rhodium catalyst, the content of reactive metal rhodium accounts for the 0.5-10% of total catalyst weight; If in the content of rhodium in reaction system, should remain in the 0.1-50mmol/L scope, preferably 1-20mmol/L.
Preparation of catalysts method of the present invention, being divided into for three steps carries out, that is: (1) is carried out free radical at 60-90 ℃ and is caused solution or suspension polymerization at first with vinyl imidazole, wherein the most frequently used is the N-vinyl imidazole, obtains ethene imidazoles homopolymer; If in ethene imidazoles monomer, add the linking agent Vinylstyrene again, then obtain cross-linking copolymer; (2) homopolymer or cross-linking copolymer are joined in the methyl iodide, perhaps again with methyl alcohol or the dilution of benzene equal solvent, the reaction backflow is 0.5-24 hour in the round-bottomed flask that agitator and condenser are housed, pressure reducing and steaming solvent or through the filtering and washing drying under reduced pressure, it is quaternised faint yellow standby to pale brown look part promptly to obtain part; (3) with above-mentioned superpolymer part that makes and four carbonyl dihalo-s, two rhodiums [Rh (CO)
2X]
2(X=Cl, Br, I) join in methyl alcohol or benzene or the mixed solvent by certain weight ratio (rhodium accounts for 0.5-10wt.% in catalyzer), under room temperature and argon shield stirring reaction 0.5-4 hour, naturally dry or remove after filtration and desolvate, drying under reduced pressure gets faint yellow extremely pale brown look polymer rhodium catalyst particle or crystal powder finished product, but places the interior prolonged preservation of moisture eliminator standby; The polymer rhodium catalyst also can original position form in reaction system, is about to the precursor compound of superpolymer part and rhodium, for example four carbonyl dihalo-s, two rhodiums or Trichlororhodium hydrate RhCl
33H
2O etc. directly join in the carbonylation reaction medium according to a certain ratio, and closed reactor is pressed into CO, in intensification or reaction process, just form described polymer rhodium catalyst automatically.Although the consumption of rhodium might not need strict restriction in the catalyzer, but generally rhodium content therein should be controlled between the 0.5-10wt%, if in the content of rhodium in reaction system, should remain in the 0.1-50mmol/L scope, preferably 1-20mmol/L.
The using method of catalyzer of the present invention, with industrial existing technology basically identical, promptly earlier with polymer rhodium catalyst (or precursor compound of superpolymer part and rhodium), material benzenemethanol (using when system acetate and methyl acetate) or methyl acetate (using during the system acetic anhydride), also has promotor, other auxiliary agent and additive join in the reactor in the room temperature metering according to a certain ratio, airtight, with twice of CO purge of gas, charge into CO again to specified carbonylation reaction pressure range, and be warmed up to specified reaction temperatures for carbonylation will interval, clock reaction, observed and recorded CO absorption rate, and get the gas sample respectively and the liquid sample is done gas chromatographic analysis.Perhaps in room temperature inflation a little earlier, fill reaction gas again after waiting to be warmed up to the assigned temperature interval, and under constant pressure air feed, clock reaction, and sampling analysis.After reaction finishes,, or cool off with ice-water bath again, open the gas of emitting before the still through gas chromatographic analysis earlier with being water-cooled to room temperature; Measure reaction solution after driving still, with gas-chromatography or again with titration measuring reaction solution composition.
The promotor that the present invention adds in carbonylation reaction system is methyl halide, particularly methyl iodide; Other auxiliary agent and the additive that add have metal-salt, and particularly metal lithium salts-lithium iodide is or/and lithium acetate, and solvent acetic acid, methyl acetate or acetic anhydride.
The methyl iodide consumption should remain between the 0.5-8mol/L, normally 1-5mol/L as with the densitometer in reaction solution; Iodide account for more than the 60mol% of the total usage quantity of halogen compounds in the reaction medium.
Metal lithium salts content in reaction solution should be preferably between the 5-15wt.% in the 1-20wt.% scope; As so that wherein metallic lithium (Li) is to the ratio (Li/Rh) of rhodium atom, this value generally is at 10-500, preferably between 60-250.
In reaction system of the present invention, what add as solvent is acetate, methyl acetate or acetic anhydride, and its effect is that not only they are fine solvents, can make that the chemical compatibility between each chief component can be better in the reaction system; Being also on the other hand that they have carbonylation reaction induces and promoter action, is very favourable to improving rate of catalysis reaction.Especially in carbonylation system acetic anhydride reaction system, their metallic compound that is beneficial to as promotor that has in a large number occurs with the acetate form, thus easier the carrying out of formation that can cause catalyzed reaction final product acetic anhydride.For carbonylation of methanol, the primary solvent of adding is an acetate, and the add-on by volume can account for the 5-90% of reaction medium, preferably is controlled in the 20-55% scope; When producing acetic anhydride, adding more is methyl acetate, and this moment, methyl acetate itself also was a raw material, and the total concn in reaction solution is controlled in the 3-8mol/L scope, and methyl acetate/acetate mol ratio should be controlled in the 1-10 scope, preferably between the 3-6.
The important difference of carbonylation legal system acetate and acetic anhydride is: the reaction medium of carbonylation system acetic anhydride, comprise that catalyst body ties up in, should be anhydrous basically; In addition, some metallic compound promotor effect in the catalyst system of acetate carbonyl system acetic anhydride, more more obvious and important than role in the carbonylation of methanol system acetic acidreaction process.
In the reaction system, CO if can remain on more than the 0.3MPa when branch is pressed in room temperature measuring, and carbonylation reaction can carry out.In reaction temperatures for carbonylation will, raw material and reaction gas total pressure scope are 2.6-8MPa in the reactor, generally are controlled at 3-6MPa, and wherein the CO dividing potential drop preferably remains on more than the 1.5MPa.
The carbonylation temperature range is 90-210 ℃, generally in reaction more than 140 ℃, can reach catalytic rate and space-time yield with industrial application value, and is wherein preferable to be controlled at the 150-180 ℃ of effect in the scope.
The present invention is to having the improvement that carbonylating catalyst and technology thereof are carried out now, and effect is significant in the following areas:
Catalyzer that the present invention formulated and system thereof both can be applicable to carbonylation of methanol and had produced acetate, also can be applicable to acetate carbonyl system acetic anhydride.When being used for carbonylation of methanol, need not to add water and hydrogen iodide in the reaction system comes rugged catalyst and active specy thereof to keep catalytic activity, so water content greatly reduces in the thick acetic acid product that initial separation is come out, thereby can save the energy consumption that is further purified product separation.Also this characteristics just change catalyst system of the present invention a little, promptly can be used for producing acetic anhydride from methyl acetate, because the reaction medium of carbonylation system acetic anhydride should be an anhydrous system.And when being used for acetate carbonyl production acetic anhydride, although it is anhydrous that reaction system requires, also do not hinder but contain the minor amount of water that comprises crystal water in the material that adds, that is the material that contains crystal water or minor amount of water can directly use with before need not work except that water treatment.
The carbonylation experimental result shows, owing on the high-polymer molecular chain, have the imidazole ring side group, and the nitrogen-atoms part is quaternized by methyl iodide on the imidazole ring side group, catalyzer of Xing Chenging and catalytic active species thereof thus, catalytic activity in reaction system, and reactant and product between chemical compatibility and thermal stability all be improved significantly, this is most important to the rhodium loss that improves the comprehensive use properties of catalyzer, reduce in catalyzed reaction and the product separation process.
From the appended example of the present invention as can be seen, adopt catalyzer of the present invention in having the reactor of good whipping appts, to carry out catalyzed reaction, can be under comparatively gentle reaction conditions, particularly in lower pressure and temperature scope, realize the carbonylation method production of acetate and acetic anhydride, the reaction total pressure is generally at 3-6MPa, and temperature of reaction can reach catalytic rate and space-time yield with enough good industrial application value more than 140 ℃.Relatively low temperature of reaction can prolong work-ing life of catalyzer, and reactor design, material are selected, reduced operation energy consumption and production safety all is favourable.In view of temperature of reaction can drop to 180 ℃ and following, the abstraction reaction product can also adopt flash process from reaction system, and uses common evaporation technique instead.Under latter instance, adopt CO gas by the base of evaporator bubbling, prevent bumping and promote evaporation to carry out, so more help protection to catalyst activity species in the mother liquor that recycles.
Adopt the catalyzer that the present invention developed to carry out carbonylation reaction, gas-liquid mixed and stir good and can keep temperature of reaction to divide and be pressed in 1.5MPa and total still is pressed under the above situation of 2.6MPa in reactor at 150-180 ℃, CO, the carbonylation of methanol product is except that acetate and methyl acetate, even additionally do not add water, the dme growing amount also can be controlled to seldom, even can not detect carbonylation reaction selectivity＞99%; And during acetate carbonyl, in the reaction system as anhydrous interference, the carbonylation reaction selectivity is 100%.The catalytic activity of catalyzer of the present invention is higher than existing similar catalyst, and no matter its stability and space-time yield with regard to carbonylation system acetate is still made acetic anhydride, all are far longer than present commercial production levels.Carbonylation of methanol is 5.26mmol/L and temperature of reaction when being 160 ℃ at rhodium concentration shown in table 1 (example 4) data, and space-time yield has promptly reached 14.9mol AcOH/Lh.
Table 1, carbonylation of methanol experiment
| Numbering | Example | Temperature ℃ | Pressure MPa | [Rh] mmol/L | [MeI] mol/L | Reaction times | MeOH transformation efficiency % | Catalytic rate a | Space-time yield b |
| 1 | 3 | 140 | 4.0 | 5.41 | 2.81 | 1h | 79.2 | 1191 | 6.4 |
| 2 | 1 | 150 | 4.0 | 3.31 | 3.54 | 1h | 87.1 | 1997 | 6.6 |
| 3 | 4 | 160 | 4.0 | 5.26 | 3.33 | 1/3h | 52.3 | 2823 | 14.9 |
| 4 | 2 | 180 | 4.0 | 1.35 | 2.78 | 1h | 65.1 | 3151 | 4.3 |
A. unit: mol AcOH/mol Rhh; B. unit: mol AcOH/Lh
And for acetate carbonylization, its space-time yield is as indicated in table 2 (example 8) result, is 5.06mmol/L and temperature of reaction when being 180 ℃ at rhodium concentration, can be up to 11.2molAcOAc/Lh.
Table 2, acetate carbonyl experiment
| Numbering | Example | Temperature ℃ | Pressure MPa | [Rh] mmol/L | [MeI] mol/L | Reaction times | AcOMe transformation efficiency % | Catalytic rate a | Space-time yield b |
| 1 | 6 | 140 | 4.0 | 1.34 | 2.85 | 1h | 14.0 | 542 | 0.72 |
| 2 | 5 | 160 | 4.0 | 3.70 | 2.72 | 1h | 62.1 | 948 | 3.5 |
| 3 | 7 | 180 | 2.8 | 1.36 | 3.58 | 1h | 42.0 | 2118 | 2.9 |
| 4 | 8 | 180 | 4.0 | 5.06 | 2.81 | 1/4h | 41.5 | 2218 | 11.2 |
A. unit: mol Ac
2O/mol Rhh; B. unit: mol Ac
2O/Lh
Catalyst system therefor of the present invention also has an advantage, and the macromolecule ligand of Here it is catalyzer imidazole ring-containing side group both can have been made the oligomer of low-molecular-weight linearity, and the catalyzer of formation is solvable fully in reaction system, is applicable to the homogeneous phase solution reaction; Also can make the copolymer ligand of high-crosslinking-degree, the catalyzer of formation is insoluble in reaction system, and is appropriate swelling, and changing homogeneous reaction is that heterogenize carries out.Under latter instance, the leakage at metal active center can be by selecting appropriate solvent and regulate superpolymer/metal ratio to reduce to minimum in the catalyzer.In homogeneous phase and heterogeneous two class catalyzer, because Heat stability is good, and contain the multiple tooth functional group that chemical compatibility can be splendid in its part, this makes them not be prone to catalyzer and the attached wall of metal thereof in catalytic reaction device, sink to the bottom with coking and be difficult to remove.
Example 1
10g poly N-vinyl imidazoles is dissolved in the 60ml methyl alcohol, adds the 25g methyl iodide again, back flow reaction 20 hours, cooling back suction filtration use methanol wash, dry must pale brown chromoresin part.With gained resin part wherein 5.0g place 20ml methyl alcohol, add 0.3270g four carbonyl dichloros two rhodiums, in stirring at room 15 minutes, place nature and dry, drying under reduced pressure, standby.
In 250ml zirconium reactor, in room temperature catalyzer 1.57g, lithium iodide 7.5g, methyl alcohol 60.0ml, methyl iodide 33.1ml, methyl acetate 45.8ml, acetate 6.0ml and water 5.1ml that to add above rhodium-containing amount be 3.25wt%, rhodium concentration is 3.31mmol/L.Logical CO is warming up to 150 ℃, keeps still and presses 4.0MPa, 500 rev/mins of stirring velocitys were reacted methanol conversion 87.1% 1 hour, methyl acetate and acetate increment are respectively 0.30mol and 0.69mol, and catalytic rate is 1997mol AcOH/mol Rhh, space-time yield 6.6mol AcOH/Lh.
More than said CO gas mean that CO purity is 92-93%, other contains CO
20.5-0.9%, H
23-4%, O
20.5-0.6%, N
21-3%, all the other are steam and denier hydrogen sulfide.The used CO source of the gas of following example all is like this.
Example 2
Poly N-ethylene imidazoles-divinylbenzene copolymer the 10g of 15% degree of crosslinking is suspended in the 80ml benzene, adds the 18g methyl iodide, back flow reaction 16 hours is filtered, with benzene washing, drying under reduced pressure; With the yellow resin part of gained wherein 5g place 25ml benzene-methyl alcohol (v/v=1: 4) mixed solvent swelling; add 0.10g four carbonyl dichloros two rhodiums, stirring reaction is 24 hours under argon shield, suction filtration; vacuum-drying, the catalyzer that makes the rhodium-containing amount and be 1.0wt% is standby.
In 250ml zirconium reactor, add above catalyzer 2.09g in room temperature, methyl alcohol 71.5ml, methyl iodide 26.0ml, methyl acetate 26.7ml, acetate 24.8ml, lithium iodide 1.15g and AcOLi2H
2O 2.83g, rhodium concentration are 1.35mmol/L.Remove in the still behind the air, connect the CO source of the gas, be warming up to 180 ℃, keep still to press 3.8-4.2MPa, 500 rev/mins of stirring velocitys were reacted 1 hour, methanol conversion 65.1%, methyl acetate and acetate increment are respectively 0.51mol and 0.13mol, and catalytic rate is counted 3151mol AcOH/mol Rhh, and space-time yield is 4.3molAcOH/Lh.
Example 3
Poly N-vinyl imidazoles-divinyl benzene copolymer the 10g of 20-40 order 34% degree of crosslinking is positioned in the 100ml methyl iodide, back flow reaction 2 hours, the unnecessary methyl iodide of filtered and recycled, drying under reduced pressure gets yellow resin ligand 1 8.5g.In 250ml zirconium reactor, add above part 2.5g, RhCl
33H
2O 252.0mg, lithium iodide 8.27g, methyl alcohol 138ml and methyl iodide 32ml; Remove in the still behind the air, fill CO to 1.5MPa, be warmed up to 140 ℃, connect the CO source of the gas again, keep still and be pressed in 2.5-3.0MPa, reacted 1 hour, blowing when temperature drops to 50 ℃, product of distillation, mother liquor is pumped back in the reactor and batching again: contain methyl alcohol 57.3ml, methyl iodide 31.0ml, methyl acetate 75.7ml, acetate 3.2ml and water 9.8ml in the reaction system, rhodium concentration is 5.41mmol/L.Connect the CO source of the gas, be warming up to 140 ℃, keep still and press 4.0MPa, 500 rev/mins of stirring velocitys were reacted methanol conversion 79.2% 1 hour, the carbonylation product amount of having a net increase of is 1.14mol, catalytic rate 1191mol AcOH/mol Rh.h, space-time yield 6.4mol AcOH/Lh.
Example 4
Drop to 50 ℃ of blowings in example 3 experiment back temperature, product of distillation, mother liquor is pumped back in the reactor and batching again: contain methyl alcohol 103.8ml, methyl iodide 37.7ml, methyl acetate 26.9ml, acetate 24ml and water 11.3ml in the reaction system, rhodium concentration is 5.26mmol/L.Connect the CO source of the gas, be warming up to 160 ℃, keep still and press 4.0MPa, reacted methanol conversion 52.3%, carbonylation product increment 0.90mol, catalytic rate 2823mol AcOH/mol Rhh, space-time yield 14.9mol AcOH/Lh 20 minutes.
Example 5
Catalyzer and preparation thereof are fully with example 1.In reaction system, contain catalyzer (rhodium content 3.25wt%) 1.57g, AcOLi 2.43g, methyl iodide 22.7ml, methyl acetate 80.6ml, acetate 18.4ml, acetic anhydride 11.6ml and water 0.7ml, rhodium concentration is 3.70mmol/L; Connect the CO source of the gas, be warming up to 160 ℃, keep still and press 4.0MPa, 500 rev/mins of stirring velocitys were reacted the moisture content completely dissolve 1 hour, methyl acetate transformation efficiency 62.1%, methyl acetate and acetate increment are respectively 0.04mol and 0.43mol, and catalytic rate is 948mol AcOAc/mol Rhh, space-time yield 3.5mol AcOAc/Lh.
Example 6
Catalyzer and preparation thereof are fully with example 2.In 250ml zirconium reactor, in catalyzer 2.09g, lithium acetate 2.4g, methyl iodide 27.0ml, methyl acetate 62.6ml, acetate 25.5ml and the acetic anhydride 36.9ml of room temperature adding rhodium content 1.0wt%, rhodium concentration is 1.34mmol/L; Connect the CO source of the gas, remove air in the still, be warming up to 140 ℃, keep still to press 4.0MPa, 500 rev/mins of stirring velocitys were reacted methyl acetate transformation efficiency 14.0% 1 hour, acetic anhydride increment 0.11mol, catalytic rate count 542mol AcOAc/mol Rhh, and space-time yield is 0.72mol AcOAc/Lh.
Example 7
Poly N-vinyl imidazoles-divinyl benzene copolymer part the 2.45g of 20-40 order 34% degree of crosslinking of example 3 preparation is put into 250ml zirconium reactor, also contain RhCl in the reaction system
33H
2O53.5mg, AcOLi2H
2O 3.8g, methyl iodide 33ml, methyl acetate 60ml, methyl alcohol 14ml, acetate 7ml and acetic anhydride 20ml; Fill in the CO displacement still behind the air, be warmed up to 160 ℃, logical CO constant voltage is at 3.5MPa, 500 rev/mins of stirring velocitys, reacted 1 hour 20 minutes, blowing analysis and the reaction solution of emitting all is pumped back in reactor when temperature drops to 60 ℃, at this moment reaction system contains methyl iodide 33.2ml, methyl acetate 81.3ml, acetate 20.2ml and acetic anhydride 14.3ml, and rhodium concentration is 1.36mmol/L.Connect the CO source of the gas, be warmed up to 180 ℃, constant voltage was reacted 1 hour at 2.8MPa, methyl acetate transformation efficiency 42.0%, and the carbonylation product amount of having a net increase of is 0.43mol, catalytic rate 2118mol AcOAc/mol Rhh, space-time yield is 2.9mol AcOAc/Lh.
Example 8
In 250ml zirconium reactor, put into the cross-linking copolymer ligand 1 .91g of example 3 preparations, RhCl
33H
2O 252.0mg and AcOLi2H
2O 6.30g, also as above-mentioned after one section carbonylation reaction environment wine is educated, blowing when temperature drops to 60 ℃, product of distillation, mother liquor is pumped back in the reactor and the reaction system of preparing burden again in contain methyl iodide 33.1ml, methyl acetate 101.4ml, acetate 28.4ml and acetic anhydride 26.1ml, rhodium concentration is 5.06mmol/L; Be warming up to 180 ℃, logical simultaneously CO keeps still and presses 4.0MPa, and 500 rev/mins of stirring velocitys were reacted 15 minutes, methyl acetate transformation efficiency 41.5%, and acetic anhydride increment 0.53mol, catalytic rate is counted 2218molAcOAc/mol Rhh, acetic anhydride space-time yield 11.2mol/Lh.
Claims (14)
1, a kind of polymer rhodium catalyst that is used for carbonylation reaction, it is characterized in that: the polymer rhodium catalyst is an imidazoles polymer rhodium catalyst, promptly on part superpolymer or oligomer molecules chain, have the imidazole ring side group, and binding rhodium active specy thus, the content of the reactive metal rhodium of institute's binding accounts for the 0.5-10% of total catalyst weight.
2, polymer rhodium catalyst as claimed in claim 1 is characterized in that nitrogen-atoms on the said imidazole ring is partly by quaternized.
3, polymer rhodium catalyst as claimed in claim 1 is characterized in that said part superpolymer or oligopolymer are meant the vinyl imidazole family macromolecule.
4, polymer rhodium catalyst as claimed in claim 3 is characterized in that homopolymer that said vinyl imidazole family macromolecule is the N-vinyl imidazole or by the multipolymer of divinyl benzene crosslinked.
5, a kind of method for making that is used for the polymer rhodium catalyst of carbonylation reaction, it is characterized in that being divided into three the step carry out: the preparation of (1) part, promptly earlier N-divinyl imidazoles is carried out free radical at 60-90 ℃ and cause solution or suspension polymerization, obtain ethene imidazoles homopolymer; Perhaps in ethene imidazoles monomer, add the linking agent Vinylstyrene, then obtain cross-linking copolymer; (2) quaternized, be about to homopolymer or cross-linking copolymer and join in the methyl iodide, perhaps again with solvent methanol or benzene dilution, reaction backflow 0.5-24 hour, pressure reducing and steaming solvent or through filtering and washing, drying under reduced pressure obtains on the imidazole ring nitrogen-atoms part by quaternised superpolymer or oligopolymer part; (3) Preparation of Catalyst is about to above part and four carbonyl dihalo-s, two rhodiums [Rh (CO)
2X]
2(X=Cl, Br I) join in methyl alcohol or benzene or the mixed solvent by the content 0.5-10wt% of rhodium in catalyzer, under room temperature and argon shield stirring reaction 0.5-4 hour, naturally dry or the filtering solvent, drying under reduced pressure, sub-rhodium catalyst particle or crystal powder finished product secure satisfactory grades; Perhaps original position forms in reaction system, precursor compound four carbonyl dihalo-s, two rhodiums or the Trichlororhodium hydrate that are about to above-mentioned part and rhodium are the 0.1-50mmol/L scope according to the content 0.5-10wt% or the content of rhodium in reaction system of rhodium in catalyzer, directly join in the carbonylation reaction system, closed reactor, be pressed into CO, in the temperature reaction process, just form described imidazoles polymer rhodium catalyst automatically.
6, a kind of method for making that is used for the polymer rhodium catalyst of carbonylation reaction as claimed in claim 5 is characterized in that the content of said rhodium in reaction system is 1-20mmol/L.
7, a kind of purposes that is used to generate the carbonylation reaction polymer rhodium catalyst of acetate, it is characterized in that catalyst levels is counted 0.5-50mmol/L with the content of rhodium in the reaction solution that comprises methyl alcohol and catalyzer in the carbonylation reaction system, the consumption of promotor remains on the 0.5-8mol/L scope with the densitometer in reaction solution, promotor in reaction solution content in the 1-20wt% scope, metallic lithium (Li) is 10-500 to the ratio of rhodium atom (Rh), and the solvent load by volume accounts for the 5-90% of reaction medium.
8, a kind of purposes that is used to generate the carbonylation reaction polymer rhodium catalyst of acetate as claimed in claim 7, it is characterized in that the content of said rhodium in reaction solution is 1-20mmol/L, the consumption of promotor is counted 1-5mol/L with the concentration in reaction solution, the content of promotor in reaction solution is 5-15wt%, metallic lithium (Li) is 60-250 to the ratio of rhodium atom (Rh), and the scope that the solvent load by volume accounts for reaction medium is 20-55%.
9, a kind of purposes that is used to generate the carbonylation reaction polymer rhodium catalyst of acetate as claimed in claim 7 is characterized in that said promotor is a methyl halide, and promotor is the metal lithium salts, and solvent is an acetate.
10, a kind of purposes that is used to generate the carbonylation reaction polymer rhodium catalyst of acetate as claimed in claim 9 is characterized in that said methyl halide is a methyl iodide; The metal lithium salts is lithium iodide or lithium acetate.
11, a kind of purposes that is used to generate the carbonylation reaction polymer rhodium catalyst of acetic anhydride, it is characterized in that catalyst levels is counted 0.5-50mmol/L with the content of rhodium in the reaction solution that comprises methyl acetate and catalyzer in the carbonylation reaction system, the consumption of promotor remains on the 0.5-8mol/L scope with the densitometer in reaction solution, promotor in reaction solution content in the 1-20wt% scope, metallic lithium (Li) is 10-500 to the ratio of rhodium atom (Rh), solvent based on methyl acetate, total concn in reaction solution is counted 3-8mol/L, and methyl acetate/acetate mol ratio is controlled at 1-10.
12, a kind of purposes that is used to generate the carbonylation reaction polymer rhodium catalyst of acetic anhydride as claimed in claim 11, it is characterized in that the content of said rhodium in reaction solution is 1-20mmol/L, the consumption of promotor is counted 1-5mol/L with the concentration in reaction solution, the content of promotor in reaction solution is 5-15wt%, metallic lithium (Li) is 60-250 to the ratio of rhodium atom (Rh), and methyl acetate/acetate mol ratio is controlled between the 3-6.
13, a kind of purposes that is used to generate the carbonylation reaction polymer rhodium catalyst of acetic anhydride as claimed in claim 11; It is characterized in that said promotor is a methyl halide, promotor is the metal lithium salts.
14, a kind of purposes that is used to generate the carbonylation reaction polymer rhodium catalyst of acetic anhydride as claimed in claim 13 is characterized in that said methyl halide is a methyl iodide, and the metal lithium salts is lithium iodide or lithium acetate.
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| CN95104298A CN1037584C (en) | 1995-05-04 | 1995-05-04 | Iminazoles-rhodium catalyst and its prepn |
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| CN95104298A CN1037584C (en) | 1995-05-04 | 1995-05-04 | Iminazoles-rhodium catalyst and its prepn |
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| CN1115688A CN1115688A (en) | 1996-01-31 |
| CN1037584C true CN1037584C (en) | 1998-03-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB9712596D0 (en) * | 1997-06-16 | 1997-08-20 | Bp Chem Int Ltd | Chemical process |
| GB9712601D0 (en) * | 1997-06-16 | 1997-08-20 | Bp Chem Int Ltd | Chemical process |
| CN100415371C (en) * | 2006-04-13 | 2008-09-03 | 西南化工研究设计院 | Catalyst system for synthesizing acetic anhydride by carbonyl under low pressure |
| CN100569788C (en) * | 2007-06-11 | 2009-12-16 | 江苏索普（集团）有限公司 | Acetic anhydride rhodium complex and its preparation method and application |
| CN114436845B (en) * | 2020-10-20 | 2024-01-30 | 中国石油化工股份有限公司 | Method for synthesizing methyl methoxyacetate by carbonylation of formaldehyde |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100883A (en) * | 1985-04-01 | 1985-12-20 | 中国科学院化学研究所 | Polymkeric substance part heterogenize rhodium catalyst and method for making thereof |
| CN85107064A (en) * | 1984-08-16 | 1987-03-04 | 联合碳化公司 | Produce the method for carboxylic acid anhydride by carboxylate methyl ester with using rhodium complex catalysts |
| CN85107542A (en) * | 1984-08-16 | 1987-05-13 | 联合碳化公司 | Produce the method for acetate esters by alcohols with using rhodium complex catalysts |
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1995
- 1995-05-04 CN CN95104298A patent/CN1037584C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85107064A (en) * | 1984-08-16 | 1987-03-04 | 联合碳化公司 | Produce the method for carboxylic acid anhydride by carboxylate methyl ester with using rhodium complex catalysts |
| CN85107542A (en) * | 1984-08-16 | 1987-05-13 | 联合碳化公司 | Produce the method for acetate esters by alcohols with using rhodium complex catalysts |
| CN85100883A (en) * | 1985-04-01 | 1985-12-20 | 中国科学院化学研究所 | Polymkeric substance part heterogenize rhodium catalyst and method for making thereof |
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