CN1053391C - Methanol carbonylation sulphur-oxygen coordinated catalyst for making acetic acid and its preparation method - Google Patents

Methanol carbonylation sulphur-oxygen coordinated catalyst for making acetic acid and its preparation method Download PDF

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CN1053391C
CN1053391C CN94100663A CN94100663A CN1053391C CN 1053391 C CN1053391 C CN 1053391C CN 94100663 A CN94100663 A CN 94100663A CN 94100663 A CN94100663 A CN 94100663A CN 1053391 C CN1053391 C CN 1053391C
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catalyzer
rhodium
acetic acid
catalyst
methanol carbonylation
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柳忠阳
潘平来
黄茂开
袁国卿
王立本
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Institute of Chemistry CAS
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Abstract

The present invention relates to a catalyst for methanol carbonylation reaction and a preparation method thereof. The catalyst is a complex with a chelating cis-dicarbonyl rhodium (I) cation structure, which is prepared by that organic matter containing sulfur and oxygen is used as ligand matched with a rhodium compound. Acetic acid and methyl acetate are prepared by methanol carbonylation under the action of methyl iodide as a cocatalyst. The catalyst has activity higher than that of a catalyst for preparing acetic acid by a low-pressure methanol carbonylation method and avoids polar solvent corrosion in reaction.

Description

The sulphur-oxygen coordinated catalyst of carbonylation of methanol system acetic acid and method for making thereof
The present invention relates to a kind of catalyzer that is used to prepare acetic acid and specially refer to the catalyzer that is used for methanol carbonylation.
Preparing acetic acid by carbonylation of methanol, is the important technology route in the present acetic acid industry, and U.S. Meng Shan (Monsanto) company uses small molecules rhodium complex (I) the anionic catalyzer of low-pressure process homogeneous phase solution method preparation as [Rh (CO) 2I 2] -N +R 4(R is alkyl, aryl), but this catalyzer instability is converted into dicarbapentaborane tetraiodo rhodium (III) easily as [Rh (CO) 2I 4] -N +R 4And lose activity, for the active centre of keeping in the entire reaction system exists, need in whole reaction system, to add a large amount of hydroiodic acid HIs and other auxiliary polar solvent, not only, product separation also make corrosion even more serious for bringing difficulty.
Make support of the catalyst [patent Sul, 108,088 (1985), patent EP 277,824 (1988)] with multipolymer and superpolymer ion exchange resin and improve the separation difficulty problem, make homogeneous reaction change heterogeneous reaction into.This class carrier and rhodium can form the complexing ring, but active obviously decline, be subjected to the thermal destruction of superpolymer, the chemical degradation influence, the Polymer Surface of rhodium comes off and makes the separation system complexity, up to the present do not use in the industrialization yet, (petrochemical complex No10 in 1981, vol.5.P301 1981) report is deposited on the solid carrier soluble rhodium compound as catalyzer, adopt the activity and the highly selective of fixed-bed type reaction can raising homogeneous rhodium catalyst, can improve the stability of catalyzer, get rid of the shortcoming of product separation difficulty, but it is serious that this method exists rhodium to run off, methyl iodide pyrolysated shortcoming.
For overcome above-mentioned rhodium run off serious, separation difficulty, the shortcoming of solvent corrosion, the present invention proposes a kind of sulfur-bearing, oxygen coordinate that is used for high speed of response of having of methyl carbonylation reaction and highly selective suitable-dicarbapentaborane rhodium (I) cationic catalyst.
The catalyzer that is used for methanol carbonylation is that employing contains sulphur, oxygen organic is the catalyzer of chelating type-suitable dicarbapentaborane rhodium (I) cationic structural of part, and its structural formula is as follows:
S → Rh in the formula, O → Rh are two kinds of different coordinate bonds,
R 1-S is mercaptan, thiophenol or sulfide group
R 1Be alkyl or aryl and derivative thereof, R 2Key between the-O is singly-bound or Multiple Bonds.Described rhodium carbonyl and S, the O organic ligand forms 4～13 yuan of chelating ring structure, and its chelating ring structure is a square plane monovalent cation structure.
X in the formula -Be BPh 4 -, I, BF 4 -, CH 3CO -, HCO 3 -Chelating type-as follows along the ring structure formula of dicarbapentaborane rhodium (I): The chelating type of sulfur-bearing, oxygen organic part is suitable-and the synthetic method of dicarbapentaborane rhodium (I) cationic catalyst is as follows:
Get the part dissolving of sulfur-bearing, oxygen organic, 1 mole part is dissolved in the acetone or methyl alcohol of 10-100 mole, is heated to 40 ℃-70 ℃, stirs 0.5～2 hour, makes it to dissolve fully, under agitation is dissolved with the methanol solution of rhodium carbonyl in 0 ℃ of-40 ℃ of dropping.(methyl alcohol: rhodium carbonyl is 50-100: after 1 mol ratio) dropwising, isothermal reaction 15-120 minute, drip again and contain the aqueous solution of concentration 2-10% precipitation agent by mass percentage, make it to precipitate fully separate out till, suction filtration, with 0 ℃ water and methyl alcohol repetitive scrubbing, to constant weight, obtain containing the catalyzer of 0.2-50% mole rhodium in reduced pressure at room temperature.Oxygen, sulphur organic ligand, rhodium carbonyl, the ratio of precipitation agent is 2: 1: 1 (mol ratio).Through infrared measurement at 1900-2300cm -1Between the characteristic peak of 4-6 terminal carbonyl is arranged, proved the existence of suitable dicarbapentaborane rhodium (I) functional group, utilized nucleus magnetic resonance and X-ray diffraction to measure and confirm that this catalyzer is the catalyzer of sulfur-bearing oxygen organic for chelating type-suitable dicarbapentaborane rhodium (I) cationic structural of part.Rhodium carbonyl solution is Rh 2(CO) 4Cl 2, Rh 2(CO) 4Br, Rh 2(CO) 4I 2, solution, precipitation agent are MBPh 4, MI, MBF 4, MSCN, M (AcO 2), M 2CO 2, M (HCO 3), (M=Li, Na, K) etc.Each precipitation agent water soluble and organic solvent.
When methyl alcohol and carbon monoxide carbonylation reaction, the catalyst dissolution of getting aforesaid method system is among methyl alcohol, and in methyl iodide impouring reactor, the ratio of its methyl alcohol and methyl iodide is 3: 1 to 8: 1 (volume ratio), charges into carbon monoxide to gauge pressure 20kg/cm 2The reaction half an hour after sampling analysis, most of methyl alcohol just transforms, after being reacted to 1 hour, methanol conversion can reach 85%, methyl iodide concentration does not change in entire reaction course, and the present invention contains sulphur, oxygen coordination chelating type never adds other any solvent or additive along in the dicarbapentaborane rhodium catalytic system.
The present invention contains sulphur, oxygen coordination chelating type, and suitable-dicarbapentaborane rhodium catalyst has following constitutional features:
(1) above-mentioned said catalyzer, wherein sulphur atom is on the strong coordination position, and Sauerstoffatom is in weak coordination position, the sulphur atom of strong coordination ability with have certain flexible carbochain and link to each other with the power of the awarding atomic oxygen of weak coordination ability, formation has S → Rh, rhodium carbonyl (1) title complex of the square plane of O → Rh coordinate bond.
(2) because chelate structure, and the existence of coordination sulphur atom by force in the chelate structure, it must have good thermostability, simultaneously because the existence of weak donor oxygen, then when the reaction addition, be easy to disassociation, and the positive monovalent cation of chelate ring and formation and the acting in conjunction of coordination anion are easy to and the oxygen relocation bit carbon monoxide after cancellation, thereby this class catalyzer has excellent chemical stability.
(3) chelate structure of catalyzer formation recited above is asymmetrical title complex, and wherein weak coordinate O → Rh is not with CH 3The I addition keeps its active coordination structure, and catalysis addition elimination reaction is carried out smoothly, thereby keeps the high reactivity and the highly selective of catalyzer.
(4) because above-mentioned catalyst structure active centre is positive monovalent cation structure, exist, make this class catalyzer have certain poison resistance as yet not by the sulphur of complexing.
(5) above-mentioned not by coordinate sulphur and CH 3I easily generates sulfonium salt, and helps the mass transfer process of catalyzer in reaction system.
(6) above-mentioned catalyzer can be loaded on the inorganic and polymer matrix, and described polymer matrix is the polymer matrix of grafted or copolymerization.
The present invention has following effect: speed of response that (1) is high and highly selective
Can be 10kg/cm in the CO dividing potential drop 2Under 100 ℃ of temperature, carry out carbonylation reaction.Under 140 ℃, the conversion rate of methyl alcohol reaches 1000g ACOH/gRh-hr, and by the methyl alcohol that transforms, the acetic acid production rate reaches 70-80%, never finds the by product as dme in reaction process, and the selectivity of its carbonylation reaction is＞99%.
(2) heat-resistant stability
The catalytic activity of catalyzer of the present invention is along with temperature of reaction raises to increase, and arriving 170 ℃ does not still have downtrending, and in high like this use temperature, other homogeneous phase small molecules rhodium catalyst is often owing to the decomposition of rhodium complex forms Rh (CO) 2I 4Lose activity, speed of response is descended, from thermogravimetric curve, catalyzer of the present invention just begins weightlessness at 190 ℃.
(3) low-corrosiveness and gentle reaction conditions
Temperature of reaction is 125-155 ℃, and the reactive system gauge pressure is 20-40kg/cm 2, stirring velocity need not to add other any solvent and additive greater than 200 rev/mins except that methyl alcohol and methyl iodide in the system, and methanol conversion just can meet and exceed the Mousanto level, CH in the reaction system 3I content does not lose, because reaction system is simple, does not need to add HI, H in the reaction mechanism simultaneously 2O isopolarity secondary solvent has relaxed the corrosion of reaction medium to equipment greatly, thereby has simplified in the past separate complex in the Monsanto technology, the big technological problems that brings of corrodibility.
Its reaction mechanism is:
(1)
(2)
(3)
(4)
(5)
(6)
Embodiment 1:
Get HS-(CH 2) 3-Si-(OCH 3) 31g, dissolving is done in the 50ml acetone, will be dissolved in 1.5g in the 20ml methyl alcohol, Rh 2(CO) 4Cl 2Drip in above-mentioned solution, be heated to 40 ℃, behind the magnetic agitation 1hr, drip the sodium tetraphenylborate aqueous solution of 2.5g, post precipitation can obtain the brownish black catalyzer.
Embodiment 2:
Get 1g is dissolved in the interior ketone of 10ml, under magnetic agitation, after making it to dissolve fully, adds the Rh of 2g 2(CO) 4I 2After the back keeps 40 ℃ to stir 20min down, drip 2% KI solution 2ml, produce precipitation immediately through washing and filtering, drying can obtain the reddish-brown catalyzer.
Embodiment 3:
Get HS (CH 2) 2-Si (OCH 3) 3Coordinate adds in the autoclave along dicarbapentaborane rhodium (I) cationic complex catalyst, in the mixture impouring still of methyl alcohol and methyl iodide (volume ratio, 6.5: 1), and its rhodium content 4 * 10 -5The mole rhodium/liter, the gauge pressure 40kg/cm of carbon monoxide 2, be warming up to 135 ℃, reacted 2 hours, methanol conversion 83%, acetate productive rate 30%, methyl acetate productive rate are 41%.
Embodiment 4
Get HS (CH 2) 3-Si-(OC 2H 5) 3Coordinate is suitable-and dicarbapentaborane rhodium (I) cationic complex catalyst adds in the autoclave, adds in the autoclave its rhodium content 3.2 * 10 with the mixture of methyl alcohol and methyl iodide mixture (volume ratio 4: 1) -5The mol rhodium/liter, make the CO gauge pressure to 40kg/cm 2, be warming up to 135 ℃ ± 5 ℃, after 3 hours, methanol conversion reaches 94%, and acetate productive rate 41%, methyl acetate are 51%.
Embodiment 5
Get
Figure C9410066300101
Coordinate is suitable-and dicarbapentaborane rhodium (I) cationic complex catalyst adds in the autoclave, and making methyl alcohol and methyl iodide ratio is 3.5: 1 (volume ratio), and making rhodium content is 5.6 * 10 -5The mol rhodium/liter, charging into carbon monoxide, to make gauge pressure be 40kg/cm 2, temperature is 140 ℃ ± 5 ℃, reacts after 3.5 hours, methanol conversion is 98%, ritalin productive rate 48%, acetic acid yield 46%.

Claims (4)

1. one kind is used for the catalyzer that methanol carbonylation prepares acetic acid and ritalin, it is characterized in that described catalyzer is that employing sulfur-bearing, oxygen organic are the catalyzer of chelating type-suitable dicarbapentaborane rhodium (I) cationic structural of part, and its structural formula is as follows:
Figure C9410066300021
Has S → Rh in the formula, two kinds of different coordinate bonds of O → Rh; R 1-S is mercaptan or sulfide group; R 2Key between the-O is singly-bound or Multiple Bonds; R 2The structural formula of-O is:
Figure C9410066300022
Or
Figure C9410066300023
X -Be BPh 4 -Or I -
2. the preparation acetic acid of methanol carbonylation and the catalyzer of ritalin of being used for according to claim 1 is characterized in that the ring texture formula of described chelating type-suitable dicarbapentaborane rhodium (I) is as follows:
Figure C9410066300024
Or
Figure C9410066300025
3. Preparation of catalysts method according to claim 1 is characterized in that 1 mole of S, and the O organic ligand is dissolved in molar ratio in the acetone of 10-100 or the methyl alcohol, and under agitation, being dissolved with rhodium carbonyl in 0 ℃ of-40 ℃ of dropping is Rh 2(CO) 4Cl 2Or Rh 2(CO) 4I 2Methanol solution, methyl alcohol: rhodium carbonyl is 50-100 in molar ratio: 1, after dropwising, isothermal reaction 15-120 minute, concentration is the aqueous solution adding of the precipitation agent of 2-10% sodium tetraphenylborate or potassiumiodide with being dissolved with by mass percentage, S, O organic ligand, above-mentioned rhodium carbonyl, the ratio of precipitation agent is 2: 1: 2 in molar ratio, treats the product post precipitation, suction filtration, with 0 ℃ water and methyl alcohol repetitive scrubbing, in reduced pressure at room temperature to constant weight.
4. the purposes of catalyzer according to claim 1 is characterized in that being used to prepare acetic acid and ritalin.
CN94100663A 1994-01-21 1994-01-21 Methanol carbonylation sulphur-oxygen coordinated catalyst for making acetic acid and its preparation method Expired - Fee Related CN1053391C (en)

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Citations (4)

* Cited by examiner, † Cited by third party
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
CN85101403A (en) * 1984-02-16 1987-01-17 Bp化学有限公司 The carbonylation method improvement
CN1060834A (en) * 1990-10-26 1992-05-06 中国科学院大连化学物理研究所 Hydro-formylation synthetic reaction with atmospheric styrene catalysing
CN1022624C (en) * 1987-01-08 1993-11-03 Bp化学有限公司 Production of carboxylic acids and esters thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85101403A (en) * 1984-02-16 1987-01-17 Bp化学有限公司 The carbonylation method improvement
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
CN1022624C (en) * 1987-01-08 1993-11-03 Bp化学有限公司 Production of carboxylic acids and esters thereof
CN1060834A (en) * 1990-10-26 1992-05-06 中国科学院大连化学物理研究所 Hydro-formylation synthetic reaction with atmospheric styrene catalysing

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