CN1117620C - Multiphase Rh-Li metal catalyst for methanol carbonylation and its prepn - Google Patents
Multiphase Rh-Li metal catalyst for methanol carbonylation and its prepn Download PDFInfo
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- CN1117620C CN1117620C CN 00129896 CN00129896A CN1117620C CN 1117620 C CN1117620 C CN 1117620C CN 00129896 CN00129896 CN 00129896 CN 00129896 A CN00129896 A CN 00129896A CN 1117620 C CN1117620 C CN 1117620C
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Abstract
The present invention relates to a rhodium-lithium double metal heterogeneous catalyst for the carbonylation reaction of methanol. The present invention is formed by adsorbing catalytic active materials, rhodium and lithium, onto carriers which are porous carbon substrates with high specific surface area, wherein the porous carbon substrate carriers with high specific surface area have the bore diameter of 8 to 12A and the specific surface area of 800 to 1000 m<2>/g, the contents of the active constituents, rhodium and lithium, are not lower than 0.1% of the catalyst by weight, and the total contents of the rhodium and the lithium are not higher than 10%. Under relatively moderate conditions, the catalyst carbonylates methanol into ethanoic acid and methyl acetate without the addition of other solvents, and the activity of the catalyst can be compared with that of catalysts in homogeneous reaction.
Description
Technical field
The present invention relates to a kind of bimetallic heterogeneous catalyst, specifically, provide a kind of loaded multiphase Rh-Li metal catalyst of carbonylation of methanol heterogeneous reaction and method for making of this catalyst of being used for.
Background technology
With Britain Bp company is that representative adopts rhodium catalyst homogeneous phase method catalysis methanol carbonyl to turn to the method for acetate, has formed very big production scale.But because the equipment of homogeneous catalyst requires complexity, the product separation difficulty, and reaction medium brings very big difficulty to the seriously corroded of equipment to industrial production in course of reaction.
Adopt the fixed bed reaction form to carry out carbonylation of methanol system acetic acidreaction, can overcome the deficiency of homogeneous process to a great extent, the researcher has carried out a large amount of experimental studies to the gas and solid phase catalyzing agent for this reason.But do not find the catalyst that can be used in suitability for industrialized production so far as yet, mainly contain three problems and do not solve.The one, do not find a kind of desirable catalyst carrier.Active carbon is catalyst carrier (the Japan Patent J59-139330 that once was considered to best, J63-233936), also has widely used silica and metal oxide carrier (Japan Patent J56-104838, J56-104839, European patent (EP276049,1988), zeolite and some inorganic salts carrier of also being used to this class catalyst uses (German patent DE 3606169,1987 years) but their activity does not all reach industrialization demands far away in addition.The 2nd, do not find a kind of method that prevents that rhodium from coming off from the carrier surface in a large number in course of reaction.This is because active carbon, the mechanical strength of catalyst carrier such as silica and metal oxide is bad or can not form stable bonding with reactive metal, the processing method of catalyst is improper simultaneously, can not make metal with than carrier surface strong bonded, cause in course of reaction, reactive metal comes off or enters the product with cutting out the powder that the surface comes off from carrier surface, causes catalytic activity to fall the end even the obstruction of reaction system occurs.The 3rd, the granule size of carrier is restive to obtain desirable single-size, the also inaccessible unification with high surface of the pore-size distribution on the particle simultaneously, the ideal performance requirement that does not promptly reach industrial catalyst as acetic acid production.In addition, in existing catalyticing research reaction system, some research work uses a certain amount of acetate to increase the conversion ratio of carbonylation of methanol with the polarity that increases system as additive, but the existence of acetate has but reduced the effective reaction space of methyl alcohol, thereby has reduced the turn over number in the unit interval.
Summary of the invention
The present invention is directed to the problems referred to above that existing heterogeneous catalyst exists, its objective is provides one to be used for multiphase Rh-Li metal catalyst for methanol carbonylation, this catalyst with the high polymer carburising substrate of high mechanical properties and high thermal stability as catalyst carrier, and an active material rhodium and a lithium compound are carried in suction, be a kind of heterogeneous catalyst that can be better than existing similar catalyst, utilize catalyst of the present invention to solve unsolved for a long time the problems referred to above to a certain extent.
For achieving the above object, the invention provides a kind of multiphase Rh-Li metal catalyst for methanol carbonylation, by porous high-ratio surface carbon matrix is that carrier is inhaled year catalytic active substance rhodium and lithium constitutes, and wherein said porous high specific surface carbon medium carrier is meant that the aperture is that 8-12A and specific area are 800-1000m
2The carbon matrix of/g, and the content of active component rhodium, lithium uneven by weight be less than catalyst 0.1%, the total content of rhodium and lithium is not more than 10% by weight.
The catalyst of the invention described above is a kind of with the carburising substrate carrier of high polymer material process carbonization formation and the methanol carbonylation bimetallic heterogeneous catalyst of rhodium and lithium strong bonded, and this catalyst has following architectural feature:
(1) with the high polymer bead of a fixed structure matrix as catalyst carrier.For example select for use vinylidene chloride or acrylonitrile to carry out polymerisation as raw material monomer, making granularity is 20-200 purpose Vingon or polyacrylonitrile bead;
(2) circle or the carbonization at high temperature of column matrix of the 1-10mm diameter that forms through machining again with above-mentioned high polymer bead or high polymer bead, make the carbonization carrier of a kind of porous and high-ratio surface, pore size on the carrier is 8-12A, specific area is the 800-1000 meters squared per gram, even pore distribution, the pore size homogeneous is the catalyst carrier of a kind of high mechanical properties and high heat stability;
(2) (wherein rhodium, lithium content all are no less than 0.1% of catalyst weight for carrier and catalytically-active metals, its total amount be not more than catalyst weight 10.0%) form the catalyst of firm bonding, be about to inhale the carbonization porous matrix that has carried rhodium and lithium compound, handle through certain high temperature, rhodium and lithium are bonded on the carrier securely.Wherein rhodium and lithium difficult drop-off experimental results show that from the carrier surface active metallic content that enters the product that comes off to be no more than 20ppb, (being generally 1-10ppb).
The method for making of methanol carbonylation bimetallic heterogeneous catalyst provided by the invention, the preparation and the Preparation of catalysts that comprise catalyst carrier, that is: (1) high polymer bead is synthetic, (2) high polymer material prepares porous high-ratio surface carbonization medium carrier through carbonization, and (3) carbonization carrier adsorption activity material rhodium and lithium compound prepare the method for high mechanical properties and high thermal stability catalyst.Specifically:
(1) preparation of high polymer bead is that high polymer monomer material sodium chloro ethylene or acrylonitrile are adopted suspension polymerization, add common radical initiator, for example ABVN or azodiisobutyronitrile, rising temperature to about 40 ℃ (vinylidene chlorides) or about 70 ℃ (acrylonitrile) carry out polymerisation under normal pressure, and it is 20-200 purpose high polymer bead that the control mixing speed makes granularity.
(2) to prepare the method for porous high-ratio surface carbonization medium carrier be to remove wherein unconverted monomer or oligomeric (impurity) with the high polymer bead or through the circular or granular high polymer of machining moulding 1-10mm diameter with solvent extraction to the carbonization of high polymer bead; then at inert gas (nitrogen; argon; helium) protection raises temperature gradually to 150-500 ℃ down; heat up and continue 5-8 hour; high polymer generating unit separation structure is decomposed; take off hydrogen chloride (from vinylidene chloride) or hydrogen cyanide (from acrylonitrile); the temperature that further raises again is to 500-1000 ℃; calcination 1-5 hour; make its carbonization, make the carbided catalyst carrier.
(3) method of carbonization carrier adsorption activity material Rh and Li compound high mechanical properties and high thermal stability catalyst is the compound with rhodium; rhodium chloride for example; four carbonyl dichloros, two rhodiums; four carbonyl diiodo-s, two rhodiums; rhodium nitrate or rhodium sulfate; and the compound of lithium; as lithium acetate; lithium hydroxide; lithium iodide or lithium chloride are dissolved in the solvent; mix with catalyst carrier that (weight ratio that metal rhodium and lithium account for catalyst is for all greater than 0.1%; and its total amount is less than 10%); make rhodium and lithium compound be adsorbed in the carbonization carrier surface; after the oven dry; with behind the hydrogen reducing under inert gas shielding the rising temperature to 300-1000 ℃; carried out calcination 1-10 hour, and made catalyst of the present invention.
In the process (2) of above-mentioned preparation, be used to extract the solvent of removing unconverted monomer or oligomer and can use the organic solvent that can dissolve high polymer monomer, for example organic solvent commonly used such as acetone, hexane, benzene or toluene.
In the process (3) of above-mentioned preparation, the solvent of the compound of dissolving rhodium and the compound of lithium can use methyl alcohol, ethanol, water or other solvent.
In addition, there is no particular limitation to the solvent for use amount in above-mentioned preparation process, be unfavorable for removing unconverted monomer (or oligomer) and be difficult to make rhodium and lithium compound evenly to be adsorbed on the carbonization carrier surface but the use amount of solvent is very few, but the solvent use amount is too much, will increase again to separate the process of desolvating of removing.General dissolving use amount (by volume) is 1-10 a times of handled thing.
In the process (3) of above-mentioned preparation, carry out with being reflected under 200-400 ℃ of hydrogen reducing metal, fully be reduced for making metal, reduction reaction should be no less than 1 hour, is generally 1-4 hour.
Above-mentioned multiphase Rh-Li metal catalyst of the present invention is used for methanol carbonylation and has high catalytic activity and selectivity: the conversion rate index at methanol carbonylation methyl alcohol surpasses 2000, (the mol product/molRh.h), conversion of methanol is 65-90% to be generally 2000-3000; Calculate by the methyl alcohol that transforms, the acetate productive rate is 55-70%, and the methyl acetate productive rate is 25-45%.
In addition, catalyst of the present invention is used for methanol carbonylation and also has following characteristics: (1) strengthens solvent hydroiodic acid and acetate etc. because it has higher activity and selectivity so need not to add polarity in reaction system; (2) this catalyst is a kind ofly to be used for methanol carbonylation to produce acetate be the catalyst of primary product, can (carbon monoxide pressure of tension is 2kg/Cm in low pressure
2More than) and the effective carbonylation of methanol catalytic reaction of the following realization of mild temperature (more than 140 ℃); (3) only use co-catalyst iodomethane and simple fixed bed type reactor or column reactor can produce acetate.Therefore, utilize its reaction unit of methanol carbonylation of catalyst of the present invention simple, corrosivity is little.
The specific embodiment
Give further detailed explanation below by embodiment to technology of the present invention.
Embodiment 1 catalyst carrier prepares I
Get commodity vinylidene chloride raw material, by 0.2% adding ABVN, and adopt suspension polymerization to carry out polymerisation under 40 ℃, control mixing speed (80-100 rev/min) obtains 20-60 height of eye polymers bead.
Acetone with 2.5 times of high polymer volumes soaked the above-mentioned high polymer bead that makes after 2 hours, the elimination solvent, and drying makes solvent evaporates.Gained high polymer bead is put into quartz ampoule be warmed up to 350 ℃ gradually under nitrogen protection, and kept 5 hours, be warmed up to 600 ℃ again, roasting 3 hours obtains the carbonization bead.Its average pore size is 8.5 after tested, and specific area is 100m
2/ g.
Embodiment 2 catalyst carriers prepare II
Get commodity propionitrile raw material, by 0.1% adding nitrogen nitrogen bis-isobutyronitrile, and adopt suspension polymerization to carry out polymerisation under 70 ℃, control mixing speed (120-130 rev/min) obtains 60-80 purpose high polymer bead.
Toluene with 1.5 times of volumes of this high polymer soaked this high polymer after 1 hour, and elimination toluene and drying make solvent evaporates.Be warmed up to 500 ℃ and kept 4 hours in quartz ampoule under argon gas atmosphere, be warmed up to 1000 ℃ again, roasting obtained the carbonization bead in 3 hours.Its average pore size is 11 after tested, and specific area is 850m
2/ g.
Embodiment 3
Quantitatively take by weighing embodiment and make 20-40 order vinylidene chloride carbonization bead carrier, take by weighing quantitative four carbonyl dichloros, two rhodiums and lithium acetate (rhodium and lithium content are respectively vehicle weight 1% and 0.5%), be dissolved in the ethanol, carrier is immersed this solution, after treating its drying, place quartz ampoule, use hydrogen reducing 1 hour down at 400 ℃, the displacement argon gas is warmed up to 500 ℃ of calcinations 6 hours, promptly makes the catalyst finished product.
Above-mentioned catalyst 4.5 is restrained in φ 6 * 300mm reaction tube of packing into, feed CO (10Kg/Cm
2) be warming up to 180 ℃, with CH
3OH and CH
3I (CH
3OH; CH
3I=10: 1 mole) mixed liquor uses compression pump with 3h
-1In the air speed input reaction tube.Collect the cooling afterproduct from the reaction column outlet.Methanol conversion is that 86% methyl alcohol from conversion calculates in the product, and the acetate productive rate is 71%, and methyl acetate is 29%, and carbonylation product space-time yield molAcoH/L.h is 20.8, to react calculating in 100 hours, rhodium loss average out to 9.2ppb.
Embodiment 4
Get embodiment 2 made polyacrylonitrile carbonization bead carrier 5 grams, (rhodium and lithium are respectively 0.8% and 0.4 bright being dissolved in ethanol and the water mixed liquid of carrier with rhodium chloride and lithium hydroxide, carrier is immersed, to be dried being placed in the quartz ampoule, 400 ℃ of hydrogen reducings 1 hour, the displacement argon gas is warmed up to 1000 ℃ of calcinations 2.5 hours, makes catalyst.
Above-mentioned catalyst 4.5 is restrained in φ 6 * 300mm reaction tube of packing into CO dividing potential drop 0.8Kg/Cm
2200 ℃ of reaction column temperatures are with methyl alcohol and iodomethane mixed liquor (CH
3OH; CH
3I=10: 1 mole) with 1.7h
-1Air speed input reaction column is collected the cooling afterproduct from the reaction column outlet.Wherein methanol conversion is 68.4%, and acetate generating rate molAcoH/molRh.h is 796.
Embodiment 5
Embodiment 1 gained Vingon bead mechanical compaction is become diameter 5mm ball-type, and 160 ℃ of cracking are 5 hours under argon shield, are warmed up to 1000 ℃ of calcinations and make the granularity requirements carrier that can use for industrialization in 2 hours.Carrier is weighed, immerse rhodium nitrate and lithium iodide solution (rhodium and lithium are respectively carrier 1.2% and 0.8%) at 300 ℃ of hydrogen reducings after 2 hours, under argon shield 900.1000 ℃ of calcinations 3 hours make catalyst.
Above-mentioned catalyst is packed in φ 40 * 1500mm reaction tube into (experiment of industry test level single tube) CO dividing potential drop 12Kg/Cm
2200 ℃ of temperature, 12: 1 moles methyl alcohol, the iodomethane mixed liquor is with 2h
-1Air speed is injected reaction column, reacts under the excessive condition of CO gas, and methanol conversion is that acetic acid content is 54% in 78% product, and methyl acetate content is 32%, in 300 hours, and rhodium loss average out to 10ppb.
Embodiment 6
Changing pure CO with 3 controlling catalysts of embodiment and reaction unit is the semiwater gas reaction, and semiwater gas each component content is CO28-30%, N
217-18%, CO
26.4-6.6%, H
244.5-46.5%, O
20.5-0.6, reaction stagnation pressure 1.2-1.3Kg/Cm
2, wherein the CO dividing potential drop is 3-4Kg/Cm
2, MeoH: MeI=1: 0.08 mole, the sample introduction liquid hourly space velocity (LHSV) is 4h
-1, 200 ℃ of reaction temperatures are calculated with 500 hourly averages, and methanol conversion is 49-50%, and acetic acid yield is 44-56%, and the methyl acetate yield is 37-41%.
Embodiment 7
By the method identical with embodiment 5, the amount that just increases lithium acetate makes rhodium and lithium content is 1% 40-60 order vinylidene chloride carbonization carried catalyst 5.9 grams, in φ 8 * 300mm reaction tube of packing into, and CO dividing potential drop 0.8Kg/Cm
2190 ℃ of reaction temperatures, the reaction mass proportioning is CO: MeoH: MeI=2: 1: 0.07CO controls with proportional valve, MeoH and MeI import with 2.2 air speeds with compression pump, are computing unit to react 10 hours, and the result is, methanol conversion is 82%, carbonylation selectivity 100%, acetic acid yield are 44-56%, and the methyl acetate yield is 37-41%, the carbonylation product generating rate is 910molAcoH/molRh.h, and space-time yield is 20.5molAcoH/L.h.
Result by the foregoing description can see, rhodium of the present invention, Li metal heterogeneous catalyst, and its preparation method is simple, and gained is used for the catalysis methanol carbonylation and produces acetate, obtains following outstanding effect: the reaction speed that (1) is high.Under gentle relatively reaction condition, the conversion of methanol index surpasses 2000, is generally 2000-3000.(2) the catalyst activity metal is from the reduction that comes off of carrier surface, and rhodium generally is no more than 10ppb from the carrier surface content that enters the product that comes off, if be used for industrial production, need not to consider the recovery problem of rhodium.(3) selectivity preferably.The primary product of reaction is an acetate, secondly is methyl acetate, also has a small amount of dimethyl ether along with the further carbonyl that gos deep into of reaction turns to acetate or methyl acetate.(4) in reaction system, need not to add the acetate equal solvent, can directly produce acetate by methyl alcohol one iodomethane.(5) in course of reaction, water gas reaction does not take place, prevented that hydrogen is to the corrosion of equipment and the consume of carbon monoxide.
Claims (5)
1. multiphase Rh-Li metal catalyst for methanol carbonylation, it is characterized in that this catalyst is that carrier is inhaled year catalytic active substance rhodium and lithium constitutes by porous high-ratio surface carbon matrix, wherein said porous high specific surface carbon medium carrier is meant that the aperture is that 8-12A and specific area are 800-1000m
2The carbon matrix of/g, and the content of active component rhodium, lithium all be no less than by weight catalyst 0.1%, the total content of rhodium and lithium is not more than 10% by weight.
2. multiphase Rh-Li metal catalyst for methanol carbonylation as claimed in claim 1 is characterized in that said carrier matrix, is Vingon or polyacrylonitrile, and its granularity is 20-200 order or ball-type or the column type that becomes the 1-10mm diameter through mechanical compaction.
3. the method for making of a methanol carbonylation bimetallic heterogeneous catalyst, it is characterized in that comprising the preparation and the Preparation of catalysts of catalyst carrier, that is: (1) high polymer bead is synthetic, (2) high polymer material prepares porous high-ratio surface carbonization medium carrier through carbonization, and (3) carbonization carrier adsorption activity material rhodium and lithium compound prepare the method for high mechanical properties and high thermal stability catalyst;
The preparation of said high polymer bead is that high polymer monomer material sodium chloro ethylene or acrylonitrile are adopted suspension polymerization, add radical initiator ABVN or azodiisobutyronitrile, rising temperature to 40 ℃ (vinylidene chloride) or 70 ℃ (acrylonitrile) carry out polymerisation under normal pressure, and it is 20-200 purpose high polymer bead that the control mixing speed makes granularity;
The method that the carbonization of said high polymer bead prepares porous high-ratio surface carbonization medium carrier is to remove wherein unconverted monomer or oligomeric (impurity) with the high polymer bead or through the circular or granular high polymer of machining moulding 1-10mm diameter with solvent extraction, then at inert gas nitrogen, the temperature that raises gradually under argon or the helium-atmosphere is to 150-500 ℃, heat up and continue 5-8 hour, high polymer generating unit separation structure is decomposed, take off hydrogen chloride (from vinylidene chloride) or hydrogen cyanide (from acrylonitrile), the temperature that further raises again is to 500-1000 ℃, calcination 1-5 hour, make its carbonization, make the carbided catalyst carrier;
The method of said carbonization carrier adsorption activity material Rh and Li compound high mechanical properties and high thermal stability catalyst is with rhodium chloride; four carbonyl dichloros, two rhodiums; four carbonyl diiodo-s, two rhodiums; rhodium nitrate or rhodium sulfate; and lithium acetate; lithium hydroxide; lithium iodide or lithium chloride are dissolved in the solvent; mix with catalyst carrier that (weight ratio that metal rhodium and lithium account for catalyst is for all greater than 0.1%; and its total amount is less than 10%); make rhodium and lithium compound be adsorbed in the carbonization carrier surface; after the oven dry; with behind the hydrogen reducing under inert gas shielding the rising temperature to 300-1000 ℃; carried out calcination 1-10 hour, and made catalyst of the present invention.
5. the method for making of methanol carbonylation rhodium lithium heterogeneous catalyst as claimed in claim 3, it is characterized in that in the said process (2) that being used to extract the solvent of removing unconverted monomer or oligomer is organic solvent-acetone, hexane, benzene or the toluene that can dissolve high polymer monomer in above-mentioned preparation; In the process (3) of above-mentioned preparation, the solvent of the compound of dissolving rhodium and the compound of lithium can use methyl alcohol, ethanol, water.
6. the method for making of methanol carbonylation rhodium lithium heterogeneous catalyst as claimed in claim 3 is characterized in that carrying out with being reflected under 200-400 ℃ of hydrogen reducing metal in the said process in above-mentioned preparation (3), and reduction reaction is 1-4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129896 CN1117620C (en) | 2000-10-24 | 2000-10-24 | Multiphase Rh-Li metal catalyst for methanol carbonylation and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129896 CN1117620C (en) | 2000-10-24 | 2000-10-24 | Multiphase Rh-Li metal catalyst for methanol carbonylation and its prepn |
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|---|---|
| CN1349852A CN1349852A (en) | 2002-05-22 |
| CN1117620C true CN1117620C (en) | 2003-08-13 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100482345C (en) * | 2004-03-25 | 2009-04-29 | 香港理工大学 | Polymer carbonizing porous matrix and its prepn and application |
| WO2017159466A1 (en) * | 2016-03-18 | 2017-09-21 | 千代田化工建設株式会社 | Vinylpyridine resin for catalyst carriers, production method therefor, and catalyst for methanol carbonylation reaction |
| CN109354137B (en) * | 2018-11-27 | 2021-07-30 | 浙江工业大学 | Preparation and application of carbon nanotube/MOF (metal organic framework) derived porous carbon composite electrode material |
| CN114849754B (en) * | 2022-04-29 | 2024-03-15 | 江苏索普化工股份有限公司 | Methanol carbonylation catalytic system based on nano carbon nitride-acetic acid dispersion liquid and preparation method and application thereof |
| CN115814833A (en) * | 2022-11-16 | 2023-03-21 | 北京化工大学 | Low-load bimetallic nano-catalyst, synthesis method and application thereof |
| CN115709072B (en) * | 2022-11-17 | 2023-08-18 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing acetic acid by catalyzing methanol carbonylation and preparation method and application thereof |
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