CN101362103A - Unidentate rhodium carbonyl complexes catalyst of carbonyl synthesis acetic acid, acetic anhydride - Google Patents
Unidentate rhodium carbonyl complexes catalyst of carbonyl synthesis acetic acid, acetic anhydride Download PDFInfo
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- CN101362103A CN101362103A CNA2008101963970A CN200810196397A CN101362103A CN 101362103 A CN101362103 A CN 101362103A CN A2008101963970 A CNA2008101963970 A CN A2008101963970A CN 200810196397 A CN200810196397 A CN 200810196397A CN 101362103 A CN101362103 A CN 101362103A
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Abstract
The invention relates to a structure form of a catalyst which is used in methanol carbonylation reaction to prepare acetic acid and in methyl acetate carbonylation reaction to prepare acetic anhydride, and a preparation method and an application thereof. The catalyst takes rhodium as the catalytically active species to form a rhodium-pyrazole coordination compound with pyrazole. The coordination compound is used in methanol carbonylation reaction to prepare acetic acid and in methyl acetate carbonylation reaction to prepare acetic anhydride and has fine catalytic activity and reaction stability.
Description
Technical field
The present invention relates to the monodentate carbonylic rhodium compound catalyst of a kind of carbonyl synthesis acetic acid, acetic anhydride, belong to Coal Chemical Industry and gas chemical industry field.
Background technology
Acetic acid is a kind of important Organic Chemicals, is mainly used in to produce VAM, aceticanhydride, terephthalic acid (TPA) (PTA), polyvinyl alcohol, acetates, cellulose acetate etc.Has extensive use in industries such as chemical industry, light textile, medicine, dyestuffs.In recent years, because the development of PTA and acetic acid downstream product, impelled acetic acid to become one of a few petroleum chemicals that output and demand increase rapidly.
BASF AG is on the basis of work such as Lei Po, the high pressure carbonylation of methanol technology of developing employing carbonyl cobalt, iodine catalyst of success, reaction temperature is about 250 ℃, and reaction pressure is 53MPa, and product yield is respectively 90% and 70% with methyl alcohol and carbonyl meter.Nineteen sixty the said firm build up in the Ludwigshafen of Germany 3.6kt/a process units and expand production capacity to 64kt/a successively.But there is the operating pressure height in this method, needs to adopt expensive resistant material, and accessory substance reaches shortcomings such as rectification flow complexity more, has only BASF Aktiengesellschaft's one covering device now in operation.
Nineteen sixty-eight, U.S. broad-mouthed receptacle for holding liquid mountain all declaration such as the Bao Like of company is developed with rhodium or iridium and is replaced cobalt to make major catalyst, is the soluble catalyst of activator with iodine, and this catalyst system and catalyzing activity is very high, reaction condition is very gentle, compare with the high pressure carbonylation method, reaction temperature is reduced to 180 ℃ by 250 ℃, and pressure is reduced to 3.5MPa by 53MPa, product is 99% with the methyl alcohol rate of collecting, count 90% with carbon monoxide, thereby be called as low-pressure process, accordingly the BASF method is called high-pressure process.
This technology is constantly improved through Celanese company, successfully developed the low water acetic acid production new technology of Celanese, its core is to add the lithium iodide of high concentration in the rhodium series catalysts, to strengthen the stability of catalyst, after adding KI and iodomethane co-catalyst, water content reduces greatly in the permission reactor, the simultaneously stable again higher reaction speed of maintenance, thereby the separation costs of new technology is reduced greatly, and increased the production capacity of reactor cleaning system.1998, Celanese company transformed the ClearLake device with this new technology, and production capacity is brought up to 1000kt/a by 450kt/a.
It is that major catalyst adds the CATIVA technology as co-catalyst such as a part of rhenium, ruthenium and osmium that BP company in 1996 develops again with metal iridium, new catalyst is under 190 ℃ of reaction temperatures and reaction pressure 2.8MPa, and reaction rate and purpose product selectivity are all higher.This technology has the following advantages: iridium catalyst system and catalyzing activity is higher than the rhodium catalyst system and catalyzing, can increase the production capacity of existing apparatus under low investment; Accessory substance is few, can operation under than the low water content condition (CATIVA technology water content＜8%, and Meng Shan all the technology water content be 14%-15%), thereby the operating cost of saving 10%-30%.This technology is used on the carbonylation of methanol system acetic acid plant of joint device of BP/Samsung company and Britain Hull company at present.In addition, foreign study the person further find, with elements such as lithium, ruthenium add iridium catalyst based in, can significantly improve carbonylation rate.
Producing in the production technology of acetic acid in carbonylation of methanol, is one of important contents to the research of catalyst.Its course of reaction is the effect that methyl alcohol passes through rhodium catalyst, prepares acetic acid with reaction of carbon monoxide, and catalyst adopts [Rh (CO)
2I
2]
-The little molecular complex of anionic [Roth, J.F.et al.Chem.Technol, 1971,600].Because this class rhodium active specy is unstable in reaction, is easy to be converted in course of reaction dicarbapentaborane tetraiodo rhodium (III) [Rh (CO)
2I
4]
-Anionic complex, and lose activity, all the more so when temperature is higher, and higher temperature is favourable to reaction.Therefore in industrial production, general employing keeps the dividing potential drop of carbon monoxide or adds the existence of excessive hydrogen iodide with protection rhodium (I) complex, but this has greatly increased the corrosiveness of reaction medium to equipment again.
At existing catalyst these deficiencies in course of reaction, people are groping the better catalyst of performance always, and hope can have advantages of high catalytic activity and better stable simultaneously.The catalyst that Britain BP company uses in recent years becomes iridium catalyst [EP 849 249,19 Dec 1996] by original rhodium catalyst, has obtained certain effect, makes catalyst performance that bigger improvement arranged.
For overcoming [Rh (CO)
2I
2]
-As the weak point of catalytic active species, researchers have carried out fruitful work, and have obtained good progress.Wherein, comparatively effective method is: adopt the little molecule contain nitrogen, phosphorus, oxygen, sulphur functional group or macromolecule ligand and Rh formation complex as catalyst, reach the purpose of improving rhodium active specy heat endurance and improving its catalytic activity.For example, adopt the part of high polymer, make catalyst when keeping higher carbonylation activity, the stability of catalyst also be improved (CN100750, US 5281359, US 6458996) as catalyst.In the research of polymer catalyst, the homogeneous phase that is part with the homopolymers and the copolymer of vinylpyridine and the research of heterogeneous reaction catalyst are always people and pay close attention to.Reported that in early days (Inor Chem.1981 (20): 64), contained the 4-vinylpyridine copolymer afterwards is part and RhCl to the catalyst that polyvinylpyridine quaternary ammonium salt anion exchange resin and rhodium reactant salt form
3The catalyst that coordination forms also is reported in media, and it adopts the homogeneous reaction form under the reaction condition of gentleness, reached higher catalysis speed (EP-0277824).Discover that the little molecule rhodium catalyst of solubility that forms with the ionic bond binding partner has the higher catalytic activity that helps, and the part of nitrogenous family element is studied and uses morely, wherein, help catalytic effect best with the pyridines quaternary ammonium salt.Think on the carbon atom of pyridines aromatic rings substituting group number and position to shorten decomposition induction time, improve initial catalytic rate effect obviously (J.Mol.Catal., 1983,20:175-184).Also there is report to point out that the variation of substituent position and character is to the formed little molecular complex of this part [[Rh (CO) on the pyridine ring in the recent period
2ClL] catalytic activity has remarkable influence (Appl.Organometal, Chem.2002; 16:258-264).
Aceticanhydride also is the basic Organic Chemicals of economic construction wilderness demand, be mainly used in the production cellulose acetate, wherein cellulose diacetate is used to make cigarette filter and plastics, Triafol T is a material of making the feeling of high class ray film, also is widely used in industries such as medicine, dyestuff, agricultural chemicals, military project, spices, medal polish.
Industrialized aceticanhydride production technology has three kinds: acetaldehyde oxidation, ketene process and methyl acetate carbonylation.Oxidation of acetaldehyde law technology source is Canadian Sha Winigan chemical company.Production technology is as follows: acetaldehyde and oxygen carry out oxidation reaction under 60 ℃, 101kPa or 70 ℃, 600-700kPa condition, with oxygen or air oxidant, be solvent with the ethyl acetate, and cobalt acetate is a catalyst, and Schweinfurt green is a promoter.Acetaldehyde and oxygen (excessive about 1%-2%) reaction at first generates Peracetic Acid, and Peracetic Acid generates aceticanhydride and acetic acid with the acetaldehyde reaction again.With this understanding, acetaldehyde conversion is 95%, and the mass ratio of aceticanhydride and acetic acid productive rate is 56:44.The total recovery of aceticanhydride is 70%-75%.By changing process conditions, can improve the productive rate of aceticanhydride.Aceticanhydride consumes acetaldehyde 1.165t per ton, standard state air 2300m
3The acetaldehyde oxidation flow process is simple, and technical maturity, but seriously corroded consume higherly, are eliminated gradually.Substituted by methyl acetate carbonylation and ketene process abroad.China's this device of Shanghai chemical reagent head factory has been in end-of-life state.
Ketene process can be divided into again according to the raw material difference: method of acetic acid and acetone method.Method of acetic acid technology source is German Wacher chemical company.Production technology is as follows: the first step, acetic acid is done under the condition of catalyst at 700-750 ℃, pressure and the 0.2%-0.3% triethyl phosphate (by the acetic acid quality) of 10-20kPa, ketenes is made in the cracking dehydration, the acetic acid conversion ratio is about 85%-90%, and the selectivity (amount of substance meter) of ketenes is about 90%-95%.Second step was that liquid acetic acid absorbs ketenes generation aceticanhydride, made the finished product aceticanhydride through rectification and purification, the conversion ratio of ketenes about 100%.This production technology is that German Wacher chemical company succeeds in developing, and realizes industrialization in 1936.The acetone method production technology is as follows: the first step is acetone at 700-800 ℃, normal pressure, does not have to carry out cracking reaction under the condition of catalyst.Second step was that liquid acetic acid absorbs ketenes generation aceticanhydride.Relative acetaldehyde oxidation of ketene process and methyl acetate carbonylating process, the flow process complexity, side reaction is many, and energy consumption is bigger, and profit is lower.Because production technology is quite ripe, the early stage abroad device of building is used this method, in China's widespread usage still.
1973, Halcon scientific development group company obtained the patent of the aceticanhydride of methyl acetate carbonylation production.Nineteen eighty-three, the said firm and U.S. Eastman-Kodak company cooperate to have built up the first cover oxo-acetic anhydride process units, and Celanese company also has this technology.Production technology is as follows: at first be that methyl alcohol and acetic acid generate methyl acetate under the sulfuric acid catalyst effect, reaction pressure is a normal pressure, and reaction temperature is 65-85 ℃, acetic acid conversion ratio about 100%.Then, methyl acetate and methyl alcohol and carbon monoxide (are 10 times of nickel catalyst because of rhodium series catalyzer to catalyse activity at iodomethane and rhodium series catalysts or nickel catalyst, therefore the industrial rhodium series catalysts that adopts) exist down morely, carry out carbonylation and generate aceticanhydride, and coproduction by acetic acid.Reaction pressure is about 2.55MPa, and reaction temperature is about 180 ℃.Its aceticanhydride/acetic acid ratio can be regulated as required.Reaction equation is:
CH
3COOH+CH
3OH→CH
3COOCH
3+H
2O；
CH
3COOCH
3+CO→(CH
3CO)
2O；
CH
3OH+CO→CH
3COOH。
Advantages such as the methyl acetate oxo synthesis has flow process weak point, good product quality, consumption is low, three waste discharge is few are being represented the advanced level of aceticanhydride production technology.At present, external main aceticanhydride supply factory all adopts this technology.Liquid phase process is than gas phase process maturation.Britain BP company has successfully developed carbonylation of methanol coproduction aceticanhydride-acetic acid technology on the basis of synthetic aceticanhydride of Halcon and Monsanto carbonylation system acetic acid technology, and realizes industrialization in 1987.Carbonylation synthesizes aceticanhydride technology, and reactor is made of esterification device and carbonylation reactor, and methyl alcohol and acetic acid generate methyl acetate at the esterification device, and methyl acetate synthesizes aceticanhydride with CO in carbonylation reactor.Owing in this process catalyst water is arranged, when generating aceticanhydride, also generates a part of acetic acid.When this technology was main to produce aceticanhydride, primary raw material was methyl alcohol, CO and acetic acid.In addition, this technology can also directly generate acetic acid with raw material CO and methyl alcohol at the carbonylation reactor internal reaction, need not through the over-churning device.Therefore, this technology can be carried out the product switching of acetic acid, methyl acetate and aceticanhydride according to the market demand.
Methanol carbonylation is produced acetic acid and methyl acetate carbonylation method and is produced the technology of the aceticanhydride part that plays the same tune on different musical instruments.The most important thing is catalyst technology in the carbonylating process technology, because the both is a carbonylation, and all is to use the rhodium series catalysts, so catalyst to a great extent can be general, promptly by changing reaction condition and separation condition, the catalyst of producing acetic acid also can be used for producing aceticanhydride.
Summary of the invention
The use characteristic of catalyst of the present invention is to be active specy with the rhodium, and iodomethane, lithium iodide are co-catalyst, under lower pressure, can utilize this catalyst carbonylation of methanol to produce acetic acid, and perhaps the methyl acetate carbonylation is produced aceticanhydride.
Producing in the method for acetic acid the invention provides carbonylation of methanol, is methyl alcohol and CO gas to be carried out methanol carbonylation obtain acetic acid under catalyst action of the present invention.Based on the reaction system gross weight, the content of catalyst in reaction system is counted 400-1200ppm with rhodium.Be preferably 600-1000ppm.
In order to improve the catalytic performance of catalyst better, catalyst also is added with co-catalyst, and described co-catalyst comprises iodomethane, lithium iodide.Wherein, the weight content of iodomethane in reaction system is 8-16%, is preferably 12-14%; The weight content of lithium iodide in reaction system is 5-20%, is preferably 8-15%.
In order to control the content of water in the reaction system, need the content of methyl acetate in the control reaction system, methanol carbonylation moves under lower water content, can reduce the load of piece-rate system.The temperature of methanol carbonylation is controlled at 170-200 ℃, is preferably 185-195 ℃.The branch of carbon monoxide is pressed in 0.2-3.5MPa, is preferably 1.0-3.0Pa.Because all gases accessory substance, and the vapour pressure of various liquid in the reaction medium, the reaction gross pressure is preferably 2.5-3.5MPa at 2.0-5.0MPa, is controlled at 3.0MPa usually.
Another purpose of invention provides the method that a kind of methyl acetate carbonylation is produced aceticanhydride.Methyl acetate can directly add reactor as reactant, also can add esterification technique production in the carbonylation reactor front portion, and this depends on the technical and economic evaluation of carrying out according to the actual conditions of manufacturer.Also methyl acetate and methyl alcohol can be come coproduction by acetic acid and aceticanhydride as mixed feeding, the output of acetic acid and aceticanhydride is than the charge ratio that can pass through to regulate methyl alcohol and methyl acetate, and the control corresponding parameter realizes.With methyl acetate and carbon monoxide is reactant, and acetic acid is solvent, and acetic acid accounts for the 30-70% (Wt) of reaction medium gross weight.Basic identical when catalyst consumption and proportioning and production acetic acid.Reaction temperature is 180-210 ℃, and reaction pressure is 3-6MPa.Reaction system also will be kept certain hydrogen partial pressure, and to keep the active valence state of rhodium catalyst, hydrogen partial pressure accounts for the 2-10% of reaction gross pressure.
This catalyst has stronger stability and high adaptability, and catalyst of the present invention can directly apply to existing low pressure methanol carbonylation method Processes for Producing Acetic Acid, and the methyl acetate carbonylation is produced the technology of aceticanhydride.It also goes for the improvement technology of existing technology, improves the structure and the type selecting that comprise nucleus equipments such as reactor and flash vessel, and the dilatation of subsequent processing device etc.
The objective of the invention is to, selection can be formed on the suitable dicarbapentaborane rhodium-pyrazole complexes of the monodentate that has good thermal stability in the air with rhodium, becomes in carbonyl is synthetic to have dynamical raw catelyst.
In catalyst structure of the present invention, its essential characteristic is that the pyrazoles that catalyst has been selected to have good stabilization in carbonyl is synthetic makes part, form metastable version with rhodium carbonyl, pyrazoles is joined trial in the reactor as promoter or stabilizing agent and be different from the common carbonylation.
The specific embodiment
In an embodiment, catalyst amount is with solid weight meter, and as dropping into the methanol solution or the acetum of catalyst, in the weight of catalyst, its methyl alcohol or acetum count the reactant inventory after converting.
Method for preparing catalyst involved in the present invention is as follows:
Embodiment 1
The pyrazoles of 1 molar part is dissolved in the methyl alcohol of 50-200 molar part, under ice bath stirs, adds [the Rh (CO) of 1/2 molar part
2Cl]
2, continue stir about after 10 minutes, in methyl alcohol, form the catalyst of structure of the present invention.Or, filter and obtain catalyst solid with excessive ether sedimentation.
Embodiment 2
Perhaps the pyrazoles with 1 molar part joins the [Rh (CO) that is dissolved with 1/2 molar part
2I]
2Acetum in, at room temperature continue to stir after 10 minutes, in acetum, form the catalyst of structure of the present invention.Or obtain catalyst solid with ether sedimentation.
When using such catalyst carbonylation of methanol to prepare acetic acid, reaction temperature is 150 ℃-200 ℃, and carbon monoxide pressure keeps 3.0-4.0MPa.When the methyl acetate carbonylation prepared acetic anhydride, reaction temperature was 170 ℃-200 ℃.Carbon monoxide and hydrogen gas mixture pressure are 3.5-4.5MPa.Wherein the content of hydrogen in mist is 1-10%.
Embodiment 3
Take by weighing the catalyst 0.3g among the embodiment 1, methyl alcohol 1.24mol, acetic acid 0.87mol, iodomethane 0.24mol, lithium iodide 0.037mol, join in the 250ml zirconium qualitative response still, reaction temperature is 170 ℃, and CO pressure is 4.0MPa, 500 rev/mins of mixing speeds, 30 minutes reaction time, methanol conversion 100%, acetic acid space-time yield 18.74mol/L.h.
Embodiment 4
Take by weighing the catalyst 0.3g among the embodiment 1, methyl alcohol 1.24mol, acetic acid 0.87mol, iodomethane 0.24mol, lithium iodide 0.052mol, join in the 250ml zirconium qualitative response still, reaction temperature is 180 ℃, and CO pressure is 4.0MPa, 500 rev/mins of mixing speeds, 20 minutes reaction time, methanol conversion 100%, acetic acid space-time yield 30.19mol/L.h.
Embodiment 5
Take by weighing the catalyst 0.3g among the embodiment 2, methyl alcohol 1.24mol, acetic acid 0.87mol, iodomethane 0.24mol, lithium iodide 0.045mol, join in the 250ml zirconium qualitative response still, reaction temperature is 160 ℃, and CO pressure is 4.0MPa, 500 rev/mins of mixing speeds, 30 minutes reaction time, methanol conversion 100%, acetic acid space-time yield 16.23mol/L.h.
Embodiment 6
Take by weighing the catalyst 0.3g among the embodiment 1, methyl acetate 0.52mol, acetic acid 0.53mol, iodomethane 0.24mol, lithium iodide 0.052mol joins in the 250ml zirconium qualitative response still, after feeding hydrogen 0.4MPa, feed CO, being warmed up to is 190 ℃, reaction constant voltage 4.0MPa, 500 rev/mins of mixing speeds, 15 minutes reaction time, methyl acetate conversion ratio 72%, aceticanhydride space-time yield 10.74mol/L.h.
Embodiment 7
Take by weighing the catalyst 0.3g among the embodiment 2, methyl acetate 0.52mol, acetic acid 0.53mol, iodomethane 0.24mol, lithium iodide 0.060mol joins in the 250ml zirconium qualitative response still, after feeding hydrogen 0.2MPa, feed CO, being warmed up to is 185 ℃, reaction constant voltage 4.0MPa, 500 rev/mins of mixing speeds, 14 minutes reaction time, methyl acetate conversion ratio 74%, aceticanhydride space-time yield 11.23mol/L.h.
Embodiment 8
Take by weighing the catalyst 0.3g among the embodiment 2, methyl acetate 0.52mol, acetic acid 0.53mol, iodomethane 0.24mol, lithium iodide 0.075mol joins in the 250ml zirconium qualitative response still, after feeding hydrogen 0.3MPa, feed C0, being warmed up to is 200 ℃, reaction constant voltage 4.0MPa, 500 rev/mins of mixing speeds, 10 minutes reaction time, methyl acetate conversion ratio 82%, aceticanhydride space-time yield 15.21mol/L.h.
Claims (7)
1, the monodentate carbonylic rhodium compound catalyst of the synthetic acetic acid of a kind of carbonylation, acetic anhydride is characterized in that with the rhodium being that active specy and pyrazoles form following coordination structure:
X=Cl or I.
2, the monodentate carbonylic rhodium compound catalyst of the synthetic acetic acid of carbonylation as claimed in claim 1, acetic anhydride is characterized in that the activity of such catalysts species are monodentate type coordination structure.
3, the monodentate carbonylic rhodium compound catalyst of the synthetic acetic acid of carbonylation as claimed in claim 1, acetic anhydride, the precursor that it is characterized in that rhodium is diiodo-four carbonyls two rhodiums [Rh (CO)
2I]
2Or dichloro four carbonyls two rhodiums [Rh (CO)
2Cl]
2
4, the monodentate carbonylic rhodium compound catalyst of the synthetic acetic acid of carbonylation as claimed in claim 1, acetic anhydride, its preparation method is as follows:
The pyrazoles of 1 molar part is dissolved in the methyl alcohol of 50-200 molar part, joins [the Rh (CO) that is dissolved with 1/2 molar part under ice bath stirs
2Cl]
2In the methanol solution or [Rh (CO)
2I]
2Acetum in, continue to stir after 10 minutes, form the described catalyst structure of claim 1, also can add excessive diethyl ether solution precipitation, filter and obtain catalyst solid.
5, catalyst as claimed in claim 4 is in the synthetic reaction of carbonylation, it is characterized in that catalyst consumption is counted with rhodium in the reaction system: rhodium content is the 200-3000PPm scope during preparation acetic acid, rhodium content is the 400-2000PPm scope during preparation acetic anhydride, and the co-catalyst iodomethane is the 0.1-5mol/L scope in reactant liquor.
6, catalyst as claimed in claim 5 is in the synthetic reaction of carbonylation, when it is characterized in that the catalytic methylester acetate carbonylation prepares acetic anhydride, add the stability that the pyrazoles part can increase reaction system in reaction system in addition, addition is the 1-500:1 scope with pyrazoles than rhodium.
7, catalyst as claimed in claim 5 is in the synthetic reaction of carbonylation, it is characterized in that catalysis is acetic acid synthesized, add lithium iodide during the acetic anhydride reaction in the system and make co-catalyst reactivity is significantly improved that its consumption is the 1-1000:1 scope with lithium than rhodium.
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Cited By (1)
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|---|---|---|---|---|
| CN103649038A (en) * | 2011-05-13 | 2014-03-19 | 诺沃梅尔公司 | Catalytic carbonylation catalysts and methods |
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2008
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103649038A (en) * | 2011-05-13 | 2014-03-19 | 诺沃梅尔公司 | Catalytic carbonylation catalysts and methods |
| US9327280B2 (en) | 2011-05-13 | 2016-05-03 | Novomer, Inc. | Catalytic carbonylation catalysts and methods |
| US10221278B2 (en) | 2011-05-13 | 2019-03-05 | Novomer, Inc. | Catalytic carbonylation catalysts and methods |
| US10479861B2 (en) | 2011-05-13 | 2019-11-19 | Novomer, Inc. | Catalytic carbonylation catalysts and methods |
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