CN101411997A - Single teeth syn-dicarbonyl rhodium-triphenylphosphine complex catalyst for carbonyl group combined to acetic acid as well as preparation method and use thereof - Google Patents
Single teeth syn-dicarbonyl rhodium-triphenylphosphine complex catalyst for carbonyl group combined to acetic acid as well as preparation method and use thereof Download PDFInfo
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Abstract
The invention belongs to the field of synthesizing acetic acid and acetic anhydride through carbonylation and relates to a catalyst of a unidentate cisdicarbonyl rhodium-triphenylphosphine composition through synthesizing acetic acid by the carbonylation of methanol and synthesizing acetic anhydride by the carbonylation of methyl acetate, and a method for preparing the catalyst and application thereof. The catalyst has excellent catalytic activity and reaction stability in catalyzing the carbonylation reaction of methanol to prepare acetic acid and the carbonylation reaction of methyl acetate to prepare acetic anhydride. Triphenylphosphine is dissolved in the methanol; under the condition of ice-bath stirring, the mixture is added into a methanol solution dissolved with rhodium tetracarbonyl chloride or an acetic acid solution dissolved with rhodium tetracarbonyl iodide and is stirred to obtain the catalyst which uses rhodium as an active species; and the rhodium active species and the triphenylphosphine form a unidentate type coordination structure with the structure.
Description
Technical field
The invention belongs to synthetic acetic acid of carbonylation and acetic anhydride field, relate to the suitable dicarbapentaborane rhodium of monodentate-triphenylphosphine complex catalyst with acetic acid synthesis from methanol carbonylation and the synthetic acetic anhydride of methyl acetate carbonylation, and these Preparation of catalysts methods and applications.
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 people's such as Lei Po working foundation, 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, the U.S. broad-mouthed receptacle for holding liquid mountain all people such as Bao Like of company is announced to develop 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 save 10%～30% operating cost.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) (III represents the valence state of rhodium) [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) (I represents the valence state of rhodium) 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 Dec1996] 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 that substituting group number and position are to shortening decomposition induction time, improving initial catalytic rate effect obviously (J.Mol.Catal., 1983,20:175～184) on the carbon atom of pyridines aromatic rings.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.
The oxidation of acetaldehyde law technology derives from 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 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→(CH3CO)
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 all on the basis of (Monsanto) carbonylation system acetic acid technology, has successfully developed carbonylation of methanol coproduction aceticanhydride-acetic acid technology on the synthetic aceticanhydride of Halcon and broad-mouthed receptacle for holding liquid mountain, and in realization 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 objective of the invention is to select can with rhodium be formed on have good thermal stability in the air monodentate along dicarbapentaborane rhodium-triphenylphosphine complex, have the monodentate of synthetic acetic acid of dynamical carbonylation and acetic anhydride along dicarbapentaborane rhodium-triphenylphosphine complex catalyst thereby be provided at carbonyl in synthetic.
A further object of the present invention provides purpose one Preparation of catalysts method.
An also purpose of the present invention provides purpose one Application of Catalyst.
The monodentate of synthetic acetic acid of carbonylation of the present invention and acetic anhydride is along the dicarbapentaborane rhodium-the triphenylphosphine complex catalyst is to be active specy with the rhodium, and this rhodium active specy and triphenylphosphine form has following monodentate type coordination structure:
X=Cl or I
(I)
The monodentate of synthetic acetic acid of carbonylation of the present invention and acetic anhydride is along dicarbapentaborane rhodium-triphenylphosphine complex Preparation of catalysts method: with the triphenylphosphine dissolved of 1 molar part in the methanol solvate of 50～200 molar part, the methanol solution that will be dissolved with triphenylphosphine under ice bath stirs joins in the methanol solution that is dissolved with dichloro four carbonyls two rhodiums 1/2 molar part or joins in the acetum that is dissolved with diiodo-four carbonyls two rhodiums 1/2 molar part, continue to stir after 10 minutes, obtain the solution of the catalyst of structural formula (I).Also can add with respect to the excessive ether solvent of structural formula (I) catalyst solution, post precipitation filters and obtains catalyst solid.
Catalyst of the present invention is when being used for acetic acid synthesis from methanol carbonylation: monodentate is joined autoclave pressure along dicarbapentaborane rhodium-triphenylphosphine complex catalyst and methyl alcohol, feed carbon monoxide, reaction temperature is 150 ℃～200 ℃, be preferably 185～195 ℃, the pressure of carbon monoxide obtains acetic acid at 3～4MPa behind the stirring reaction; Wherein, monodentate is counted 200～3000PPm along the content of dicarbapentaborane rhodium-triphenylphosphine complex catalyst with rhodium in reaction system, is preferably 400～1500ppm.
In order to improve the catalytic performance of catalyst better, in above-mentioned reaction system, can also add co-catalyst, described co-catalyst comprises iodomethane and lithium iodide.Wherein, the weight percent content of iodomethane in reaction system is 8～16%, and preferred weight percent content is 12～14%; The weight percent content of lithium iodide in reaction system is 5～20%, and preferred weight percent content is 8～15%.
When catalyst of the present invention synthesized acetic anhydride at the catalytic methylester acetate carbonylation: with methyl acetate and carbon monoxide was reactant, and acetic acid is solvent; Monodentate is joined in the autoclave pressure along dicarbapentaborane rhodium-triphenylphosphine complex catalyst, methyl acetate and acetate solvate, feeding carbon monoxide continues to feed carbon monoxide and add hydrogen after with air displacement in the autoclave pressure, reaction temperature is 180 ℃～210 ℃, obtains acetic anhydride behind the stirring reaction; Monodentate is counted 400～2000PPm along dicarbapentaborane rhodium-triphenylphosphine complex catalyst consumption with rhodium in reaction system, and acetic acid accounts for 30～70wt% of reaction medium gross weight; The reaction gross pressure is 3～6MPa, also will keep certain hydrogen partial pressure in the reaction system, and to keep the active valence state of rhodium catalyst, hydrogen partial pressure accounts for 2～10% of reaction gross pressure.
When the synthetic acetic anhydride of above-mentioned methyl acetate carbonylation, in reaction system, also can add the stability that a certain amount of triphenylphosphine ligand can increase reaction system in addition, the addition of triphenylphosphine ligand is a triphenylphosphine than the mol ratio of rhodium is 1～500:1 scope.
In above-mentioned reaction system, add co-catalyst in addition, can obviously improve reactivity.Described co-catalyst comprises iodomethane and lithium iodide.Wherein, the weight percent content of iodomethane in reaction system is 8～16%, and preferred weight percent content is 12～14%; The weight percent content of lithium iodide in reaction system is 5～20%, and preferred weight percent content is 8～15%.
The reactant methyl acetate can directly join in the 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 acetic anhydride as mixed feeding, the output of acetic acid and acetic anhydride is than realizing by the control parameters such as charge ratio of regulating methyl alcohol and methyl acetate.
Catalyst of the present invention 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.
In catalyst structure of the present invention, its essential characteristic is that the triphenylphosphine that catalyst has been selected to have good stabilization in carbonyl is synthetic makes part, form metastable version with rhodium carbonyl, triphenylphosphine 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 consumption 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.
Embodiment 1
With the triphenylphosphine dissolved of 1 molar part in the methanol solvate of 50～200 molar part, the methanol solution that will be dissolved with triphenylphosphine under ice bath stirs joins in the methanol solution that is dissolved with 1/2 molar part dichloro, four carbonyls, two rhodiums, continue to stir after 10 minutes, obtain the solution of the catalyst of structural formula of the present invention (I).Add with respect to the excessive ether solvent of structural formula of the present invention (I) catalyst solution, post precipitation filters the catalyst solid that obtains structural formula of the present invention (I) again.
Embodiment 2
With the triphenylphosphine dissolved of 1 molar part in the methanol solvate of 50～200 molar part, the methanol solution that will be dissolved with triphenylphosphine under ice bath stirs joins in the acetum that is dissolved with 1/2 molar part diiodo-, four carbonyls, two rhodiums, continue to stir after 10 minutes, obtain the solution of the catalyst of structural formula of the present invention (I).Add with respect to the excessive ether solvent of structural formula of the present invention (I) catalyst solution, post precipitation filters the catalyst solid that obtains structural formula of the present invention (I) again.
Embodiment 3
When using the catalyst carbonylation of methanol of embodiment 1 or 2 to prepare acetic acid, monodentate is joined in the autoclave pressure along dicarbapentaborane rhodium-triphenylphosphine complex catalyst and methyl alcohol, feed carbon monoxide, reaction temperature is 150 ℃～200 ℃, the pressure of carbon monoxide obtains acetic acid at 3.0～4.0MPa behind the stirring reaction; Wherein, monodentate is counted 200～3000PPm along the content of dicarbapentaborane rhodium-triphenylphosphine complex catalyst with rhodium in reaction system.
When the methyl acetate carbonylation prepares acetic anhydride, monodentate is joined in the autoclave pressure along dicarbapentaborane rhodium-triphenylphosphine complex catalyst, methyl acetate and acetate solvate, feeding carbon monoxide continues to feed carbon monoxide and add hydrogen after with air displacement in the autoclave pressure, reaction temperature is 180 ℃～210 ℃, obtains acetic anhydride behind the stirring reaction; Monodentate is counted 400～2000PPm along dicarbapentaborane rhodium-triphenylphosphine complex catalyst consumption with rhodium in reaction system, and acetic acid accounts for 30～70wt% of reaction medium gross weight; Carbon monoxide and hydrogen gas mixture pressure are 3.5～4.5MPa.Wherein hydrogen partial pressure accounts for 2～10% of reaction gross pressure.
Embodiment 4
Take by weighing the catalyst 0.38g among the embodiment 1, methyl alcohol 1.24mol, acetic acid 0.87mol, iodomethane 0.24mol, lithium iodide 0.037mol joins in the 250ml zirconium qualitative response still, feeds CO, reaction temperature is 165 ℃, CO pressure is 4.0MPa, 500 rev/mins of mixing speeds, 30 minutes reaction time, methanol conversion 100%, acetic acid space-time yield 14.23mol/L.h.
Embodiment 5
Take by weighing the catalyst 0.38g among the embodiment 1, methyl alcohol 1.24mol, acetic acid 0.87mol, iodomethane 0.24mol, lithium iodide 0.052mol joins in the 250ml zirconium qualitative response still, feeds CO, reaction temperature is 175 ℃, CO pressure is 4.0MPa, 500 rev/mins of mixing speeds, 20 minutes reaction time, methanol conversion 100%, acetic acid space-time yield 23.21mol/L.h.
Embodiment 6
Take by weighing the catalyst 0.38g among the embodiment 2, methyl alcohol 1.24mol, acetic acid 0.87mol, iodomethane 0.24mol, lithium iodide 0.045mol joins in the 250ml zirconium qualitative response still, feeds CO, reaction temperature is 165 ℃, CO pressure is 4.0MPa, 500 rev/mins of mixing speeds, 30 minutes reaction time, methanol conversion 100%, acetic acid space-time yield 18.17mol/L.h.
Embodiment 7
Take by weighing the catalyst 0.38g 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, continue to feed carbon monoxide, being warmed up to is 185 ℃, reaction constant voltage 4.0MPa, 500 rev/mins of mixing speeds, 15 minutes reaction time, methyl acetate conversion ratio 72%, aceticanhydride space-time yield 9.24mol/L.h.
Embodiment 8
Take by weighing the catalyst 0.38g 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, continue to feed carbon monoxide, being warmed up to is 190 ℃, reaction constant voltage 4.0MPa, 500 rev/mins of mixing speeds, 14 minutes reaction time, methyl acetate conversion ratio 74%, aceticanhydride space-time yield 10.85mol/L.h.
Embodiment 9
Take by weighing the catalyst 0.38g 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, continue to feed carbon monoxide, 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 16.14mol/L.h.
Embodiment 10
Take by weighing the catalyst 0.38g among the embodiment 2, methyl acetate 0.52mol, acetic acid 0.53mol, iodomethane 0.24mol, lithium iodide 0.052mol, triphenylphosphine 0.12mol, join in the 250ml zirconium qualitative response still, behind the feeding hydrogen 0.4MPa, continue to feed carbon monoxide, be warmed up to is 190 ℃, reaction constant voltage 4.0MPa, 500 rev/mins of mixing speeds, 10 minutes reaction time, methyl acetate conversion ratio 78%, aceticanhydride space-time yield 11.25mol/L.h.
Claims (9)
1. the monodentate of synthetic acetic acid of a carbonylation and acetic anhydride is along dicarbapentaborane rhodium-triphenylphosphine complex catalyst, and it is characterized in that: this catalyst is to be active specy with the rhodium, and this rhodium active specy has following monodentate type coordination structure with triphenylphosphine formation:
X=Cl or I.
2. a carbonylation according to claim 1 synthesizes the monodentate of acetic acid and acetic anhydride along dicarbapentaborane rhodium-triphenylphosphine complex Preparation of catalysts method, it is characterized in that: with the triphenylphosphine dissolved of 1 molar part in the methanol solvate of 50～200 molar part, the methanol solution that will be dissolved with triphenylphosphine under ice bath stirs joins in the methanol solution that is dissolved with dichloro four carbonyls two rhodiums 1/2 molar part or joins in the acetum that is dissolved with diiodo-four carbonyls two rhodiums 1/2 molar part, continue to stir, obtain the solution of catalyst.
3. preparation method according to claim 2 is characterized in that: add the ether solvent excessive with respect to catalyst solution in the solution of the catalyst that obtains, post precipitation filters and obtains catalyst solid.
An application rights require synthetic acetic acid of 1 described carbonylation and acetic anhydride monodentate along dicarbapentaborane rhodium-triphenylphosphine complex catalyst when being used for acetic acid synthesis from methanol carbonylation: monodentate is joined autoclave pressure along dicarbapentaborane rhodium-triphenylphosphine complex catalyst and methyl alcohol, feed carbon monoxide, reaction temperature is 150 ℃～200 ℃, the pressure of carbon monoxide obtains acetic acid at 3～4MPa behind the stirring reaction; Wherein, monodentate is counted 200～3000PPm along the content of dicarbapentaborane rhodium-triphenylphosphine complex catalyst with rhodium in reaction system.
5. application according to claim 4 is characterized in that: monodentate is counted 400～1500ppm along the content of dicarbapentaborane rhodium-triphenylphosphine complex catalyst with rhodium in reaction system.
6. according to claim 4 or 5 described application, it is characterized in that: in reaction system, add co-catalyst iodomethane and lithium iodide; Wherein, the weight percent content of iodomethane in reaction system is 8～16%; The weight percent content of lithium iodide in reaction system is 5～20%.
The application rights monodentate that requires synthetic acetic acid of 1 described carbonylation and acetic anhydride along dicarbapentaborane rhodium-triphenylphosphine complex catalyst when the synthetic acetic anhydride of catalytic methylester acetate carbonylation: monodentate is joined in the autoclave pressure along dicarbapentaborane rhodium-triphenylphosphine complex catalyst, methyl acetate and acetate solvate, feeding carbon monoxide continues to feed carbon monoxide and add hydrogen after with air displacement in the autoclave pressure, reaction temperature is 180 ℃～210 ℃, obtains acetic anhydride behind the stirring reaction; Monodentate is counted 400～2000PPm along dicarbapentaborane rhodium-triphenylphosphine complex catalyst consumption with rhodium in reaction system, and acetic acid accounts for 30～70wt% of reaction medium gross weight; The reaction gross pressure is 3～6MPa, and hydrogen partial pressure accounts for 2～10% of reaction gross pressure.
8. application according to claim 7 is characterized in that: add triphenylphosphine ligand in reaction system, the addition of triphenylphosphine ligand is a triphenylphosphine than the mol ratio of rhodium is 1～500:1 scope.
9. according to claim 7 or 8 described application, it is characterized in that: in reaction system, add co-catalyst iodomethane and lithium iodide; Wherein, the weight percent content of iodomethane in reaction system is 8～16%; The weight percent content of lithium iodide in reaction system is 5～20%.
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| CN112898149A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst |
| CN114534782A (en) * | 2022-01-17 | 2022-05-27 | 中国科学院大连化学物理研究所 | Porous organic ionic polymer, load monoatomic Rh catalyst thereof, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109453815A (en) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | The rhodium base catalyst of organic load of polymer support containing phosphine and its preparation 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 |
| CN112898149A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst |
| CN114534782A (en) * | 2022-01-17 | 2022-05-27 | 中国科学院大连化学物理研究所 | Porous organic ionic polymer, load monoatomic Rh catalyst thereof, and preparation method and application thereof |
| CN114534782B (en) * | 2022-01-17 | 2023-08-08 | 中国科学院大连化学物理研究所 | Porous organic ion polymer, single-atom Rh-loaded catalyst and preparation method and application thereof |
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