CN101600678A - The method of Fatty Alcohol(C12-C14 and C12-C18) and/or its reactive derivatives carbonylation - Google Patents
The method of Fatty Alcohol(C12-C14 and C12-C18) and/or its reactive derivatives carbonylation Download PDFInfo
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- CN101600678A CN101600678A CNA2006800566291A CN200680056629A CN101600678A CN 101600678 A CN101600678 A CN 101600678A CN A2006800566291 A CNA2006800566291 A CN A2006800566291A CN 200680056629 A CN200680056629 A CN 200680056629A CN 101600678 A CN101600678 A CN 101600678A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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Abstract
Contain C
1-C
3The product of aliphatic carboxylic acid or corresponding esters is prepared, and the preparation method comprises C
1-C
3Fatty Alcohol(C12-C14 and C12-C18) or its reactive derivatives and carbon monoxide react in the presence of zeolite catalyst, this zeolite catalyst have with by having interconnective 8 membered ring channels in duct that limit more than or equal to 8 yuan ring, these 8 yuan of rings have window size and at least one Bronsted acidity position of at least 2.5 * at least 3.6 , and this zeolite has silicon-dioxide: X
2O
3Ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
Description
Background of invention
The present invention relates to a kind of by carbonylation by corresponding lower aliphatic alcohols and/or its ester or ether derivant, selectivity prepares the method for lower alphatic carboxylic acid and/or its corresponding esters, is especially prepared the method for acetic acid and/or ritalin by methyl alcohol and/or its ester or ether derivant carbonylation selectivity.The invention still further relates to and a kind ofly more generally relate to carbonylation from the improving one's methods of dimethyl ether production ritalin, the alkyl ester of preparation aliphatic carboxylic acid by alkyl oxide.In another aspect of this invention, relate to by at first preparing alkyl ester by lower alkyl ether, then this ester is hydrolyzed into acid, thus the preparation lower alphatic carboxylic acid.A preparation that embodiment is an acetic acid like this, it forms ritalin by the dme carbonylation, and then the ester hydrolysis prepares acetic acid.
Preparation acetic acid the most widely used commercial run is carbonylation of methanol, and it for example is generally described in, English Patent 1,185,453,1,277,242 and US patent 3,689,533 in.In the method for the sort of type, methyl alcohol and carbon monoxide or contain the gas of carbon monoxide, in the presence of the catalyzer of rhodium-containing or iridium, reaction under the promotor that also has halogen-containing (normally iodine).Though be extensive use of, because the existence of iodide, these methods need be used expensive corrosion resisting alloy, and cause producing be difficult on a small quantity to utilize that conventional distillation removes contains the iodine by product from acetic acid.After deliberation some be used for the catalyst system based on non-halogen thing of this reaction, but it is not by commercialization, mainly is because its catalytic life and selective problems.
In the method that a large amount of patents are described, the mixture of methyl alcohol or methyl alcohol and dme carries out carbonylation in the presence of catalyzer.Usually this product is the mixture of acetic acid and ritalin, also comprises acetic anhydride sometimes.Disclose a reaction that can take place in these patents, promptly the dme carbonylation forms ritalin.
EP-A-0596632 disclose by in load copper, nickel, iridium, rhodium or cobalt mordenite catalyst in the presence of, Fatty Alcohol(C12-C14 and C12-C18) or its reactive derivatives contacted under high temperature and high pressure with carbon monoxide, thereby prepare the method for aliphatic carboxylic acid.
WO2005/105720 disclose by in load copper, nickel, iridium, rhodium or cobalt with silicon, aluminium and one or more gallium, boron and iron as in the presence of the mordenite catalyst of backbone element, Fatty Alcohol(C12-C14 and C12-C18) and/or its reactive derivatives are contacted with carbon monoxide, thereby prepare the method for aliphatic carboxylic acid, its ester or acid anhydrides.
US6,387,842 disclose by in the presence of the catalyzer that contains solid superacid, clay, zeolite or molecular sieve, the charging and the carbon monoxide of alcohol, ether and/or ether alcohol reacted under certain temperature and pressure, thereby be converted to the method and the catalyzer of OXO products.
Cheung etc. (Angew.Chem.Int.Ed2006,45, (10), 1617) carry out carbonylation at dme with mordenite, ferrierite and ZSM-5, BEA with under the USY zeolite contacts.The three kinds of zeolites in back do not contain 8 membered ring channels.
Summary of the invention
The present invention includes selectivity and prepare C
1-C
3Aliphatic carboxylic acid, for example acetic acid and/or corresponding C
1-C
3Ester, as the method for ritalin, it is by making corresponding C
1-C
3Fatty Alcohol(C12-C14 and C12-C18), methyl alcohol for example, and/or its ester or ether derivant, dme for example, containing carbonylation in the presence of the catalyzer of zeolite with carbon monoxide, this zeolite has at least one 8 membered ring channel, described 8 membered ring channels with interconnect by having the duct that limits more than or equal to 8 yuan ring, described 8 yuan of rings have at least 2.5
* at least 3.6
Window size and at least one Bronsted acidity position, and wherein this zeolite has silicon-dioxide: X
2O
3Ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
The present invention also comprises and contains C
1-C
3The C of aliphatic carboxylic acid
1-C
3The product of alkyl ester, ritalin for example, the preparation method, it comprises makes C
1-C
3Alkyl oxide, for example dme and carbon monoxide are under anhydrous basically environment, in the presence of the catalyzer that contains zeolite, carry out carbonylation with at least one 8 membered ring channel, described 8 membered ring channels with interconnect by having the duct that limits more than or equal to 8 yuan ring, described 8 yuan of rings have at least 2.5
* at least 3.6
Window size and at least one Bronsted acidity position, and wherein this zeolite has silicon-dioxide: X
2O
3Ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
Detailed Description Of The Invention
The present invention includes selectivity and prepare C
1-C
3Aliphatic carboxylic acid, for example acetic acid and/or ester accordingly, as the method for ritalin, it is by making corresponding C
1-C
3Fatty Alcohol(C12-C14 and C12-C18), for example methyl alcohol and/or its ester or ether derivant, dme for example, with carbon monoxide carbonylation in the presence of the catalyzer that contains zeolite with at least one 8 membered ring channel, described 8 membered ring channels with interconnect by having the duct that limits more than or equal to 8 yuan ring, described 8 yuan of rings have at least 2.5
* at least 3.6
Window size and at least one Bronsted acidity position, and wherein this zeolite has silicon-dioxide: X
2O
3Ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
The present invention also comprises and contains C
1-C
3The C of aliphatic carboxylic acid
1-C
3The product of alkyl ester such as the preparation method of ritalin, it comprises makes C
1-C
3Alkyl oxide, dme and carbon monoxide carbonylation in the presence of the catalyzer that is containing zeolite under the anhydrous basically environment for example with at least one 8 membered ring channel, described 8 membered ring channels with interconnect by having the duct that limits more than or equal to 8 yuan ring, described 8 yuan of rings have at least 2.5
* at least 3.6
Window size and at least one Bronsted acidity position, and wherein this zeolite has silicon-dioxide: X
2O
3Ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
In a mode of the present invention, a component in this method charging can be C
1-C
3Fatty Alcohol(C12-C14 and C12-C18).This method is particularly useful for alcohol, for example methyl alcohol, ethanol and n-propyl alcohol.Preferred alcohol is methyl alcohol.Can or be additional to pure pure reactive derivatives as pure surrogate and comprise ester and the C that this is pure
1-C
3The ether derivant of alcohol.Suitable reactive derivatives of methanol comprises ritalin and dme.Can also use the mixture of pure and mild its reactive derivatives, for example the mixture of methyl alcohol and ritalin.
When using alcohol as the charging of this method, product depends on the transformation efficiency that this is pure.If transformation efficiency is 100%, product is exactly a corresponding carboxylic acid.Therefore, when methyl alcohol was pure charging, this product comprised acetic acid.If transformation efficiency is less than 100%, then alcohol is converted into the mixture of corresponding carboxylic acid and carboxylicesters.If as the ester of charging is symmetrical ester, ritalin for example, then the primary product of this carbonylation method is corresponding carboxylic acid (being acetic acid in this example).If this ester is asymmetric, then product comprises the mixture of carboxylic acids from each alkyl formation of this ester.
In the other mode of the present invention, a component in this method charging comprises C
1-C
3Alkyl oxide, promptly have the compound of following formula:
R
1-O-R
2
Wherein, R
1And R
2Be C independently
1-C
3Alkyl.At R
1And R
2If the sum of carbon atom in the group is R
1And R
2Being alkyl, is 2-6.Preferred R
1And R
2Be straight chained alkyl, most preferably have the straight chained alkyl of 1-3 carbon atom respectively, for example methyl, ethyl and n-propyl.
If this ether is symmetrical ether, dme for example, then primary product is the corresponding alkyl ester of aliphatic carboxylic acid (being ritalin in this example).If ether is asymmetric, then product comprises these two kinds of possible carboxylicesterss one or both of, and this depends on that in reaction which is ruptured in two C-O keys.For example, if charging is methyl ethyl ether (R
1=methyl, R
2=ethyl), then product comprise vinyl acetic monomer and/methyl propionate.
Second component of this method is the charging that comprises carbon monoxide.This charging can comprise pure basically carbon monoxide (CO), for example, carbon monoxide is normally provided by the supplier of industrial gas, or this charging can comprise and can not hinder alkyl oxide to be converted into the impurity of required ester, for example hydrogen, nitrogen, helium, argon, methane and/or carbonic acid gas.For example, charging can comprise common utilization from synthetic gas via low temperature separation process and/or use film to remove the method for hydrogen and the carbon monoxide of commercialization preparation.
The carbon monoxide charging can comprise a large amount of hydrogen.For example, this charging can be known synthetic gas, promptly is used for any of a large amount of gaseous mixture of synthetic various organic or inorganic compound, especially ammonia synthesiss.Synthetic gas obtains by the carbonaceous material of richness and steam (in being called as the method for steam reformation) or with the reaction (method of partial oxidation) of steam and oxygen usually.These gases mainly comprise and contain carbon monoxide and hydrogen, can also comprise more a spot of carbonic acid gas and nitrogen.Carbon monoxide: the suitable molar ratio of hydrogen can be 1: 3-15: 1, for example 1: 1-10: 1.Use the ability of synthetic gas to provide another advantage, promptly select to utilize not have so expensive carbon monoxide charging than the method for preparing acetic acid from methyl alcohol.In the method for methyl alcohol-acetic acid, comprise hydrogen in the charging and may cause producing unwanted hydrogenation.
The catalyzer that uses in the inventive method is a zeolite, mordenite and ferrierite.Zeolite is natural or synthetic all is to have the microporosity crystal type alumino-silicate materials of being measured by X-ray diffraction that definite crystalline structure is arranged.The compound composition of zeolite can alter a great deal, but they are usually by SiO
2Form, wherein the part Siliciumatom can be by quadrivalent atom, as Ti or Ge, and triad, as Al, B, Ga, Fe, or bivalent atom, replace as Be or its combination.Zeolite by can with other channel system or for example the system in the interconnected duct, hole of side pocket or cage form.This channel system has uniform-dimension in specific zeolite inside, and can be three-dimensional, but not necessarily, also can be two dimension or one dimension.The channel system of zeolite arrives via 12 yuan of rings, 10 yuan of rings or 8 yuan of rings usually.The zeolite that uses among the present invention comprises the duct that at least one 8 yuan rings limit.Preferred zeolite is those zeolites that do not have side pocket or cage in zeolite structured inside.Atlas of Zeolite Framework Types (C.Baerlocher, W.M.Meier, D.H.Olson, the 5th edition, Elsevier, Amsterdam, 2001) together with based on the version of webpage (
Http:// www.iza-structure.org/ databases/) be about the topology of zeolite framework and the summary of CONSTRUCTED SPECIFICATION, comprise type that is present in ring structure in the zeolite and the duct size that is limited by each annular.For the purposes of the present invention, term " zeolite " also comprises the material with zeolite type structure, and for example layered porous crystal type oxide material and column layering oxide material are as ITQ-36.
The zeolite that uses in the inventive method has at least one 8 yuan of duct that ring limits by tetrahedral coordination atom (tetrahedron), and the minimum size that the window size of ring has is 2.5
* 3.6
The duct of these 8 yuan of rings and at least one are equal to or greater than 8 yuan by having, and interconnect as the duct that ring limited of 10 yuan and/or 12 yuan.8,10 and 12 membered ring channels of interconnection provide the inlet that leads to the Bronsted acidity position that is contained in 8 membered ring channels, make C
1-C
3Pure or derivatives thereof for example methyl alcohol and dme can carry out carbonylation under acceptable ratio.
The zeolite that uses among the present invention can be by interconnection, and only the ducts that limited by 8 yuan of rings are formed, and the zeolite of CHA type skeleton for example is as the zeolite of chabazite and ITE type skeleton, as ITQ-3.Yet preferably this zeolite has at least one by 8 yuan of ducts of forming of ring and at least one interconnection, by having greater than 8 yuan, and 10 and/or 12 yuan the duct that ring limited for example.Not restrictive example with zeolite of 8 membered ring channels and interconnective bigger annular distance road system comprises the zeolite of OFF type skeleton, offretite for example, GME type, for example sarcolite, the MFS type, ZSM-57 for example, EON type, as ECR-1 and ETR type, as ECR-34.The zeolite that uses in preferred the inventive method has at least one and at least one interconnective 8 membered ring channels of 12 membered ring channels, and the zeolite of those OFF and GME type skeleton for example is as offretite and sarcolite.
Yet in order to develop a kind of effective carbonylation method, it is not enough only having 8 membered ring channels of interconnection in zeolite.The window size of this channel system also must be controlled, and makes reactant molecule can freely spread and leave this zeolite framework.If the minimum size of the hole (hole width) of 8 membered ring channels of discovery zeolite is 2.5 * 3.6 now
The time, can realize effective carbonylation.The duct size of zeolite framework type can for example found among the Atlas of Zeolite Framework Types.In addition, M.D.Foster, I.Rivin, M.M.J.Treacy and O.Delgado Friedrichs are in " A geometric solution to thelargest-free-sphere problem in zeolite frameworks " Microporous and MesoporousMaterials 90 (2006) 32-38, used the Delaunay trigonometry to be applied on the known zeolite framework, and-spherical diameter free along the maximum of three that are used for 165 zeolite framework that are listed in the Atlas of Zeolite Framework Types at present main crystallization directions diffusions made form.The window size of ring can be changed by the atomic substitutions that is fit to, and it changes the bond distance and the bond angle of tetrahedral coordination atom and bridge joint oxygen.
Selecting from The Atlas of Zeolite Framework Types, to have at least one minimum size be 2.5 * 3.6
The part form of zeolite framework type of interconnection 8 membered ring channels list following:
Zeolite can obtain from commercial source.They can also be synthetic with known technology.Usually, synthetic zeolite is from comprising the aqueous reaction mixture preparation in suitable oxidizing thing source.In order to influence prepare zeolite, in reaction mixture, can also comprise organic directed agents with desired structure.After the component of reaction mixture suitably is mixed with each other, reaction mixture is placed suitable crystallization condition.After the complete crystallization of reaction mixture, can from remaining reaction mixture, reclaim crystallized product.This recovery can comprise filters this crystallization, calcination processing at high temperature after the washing.The synthetic of zeolite is described in a large amount of reference.For example, Y zeolite and the synthetic US 3,130 that is described in thereof, in 007, the ZSM-23 zeolite is described in US 4,076, and 842 and J.Phys.Chem.B, 109,652-661 (2005), Zones, S.I.Darton, R.J., Morris, R and Hwany are among the S-J; ECR-18 is described in Microporous Mesoporous Mat., and 28,233-239 (1999), Vaughan D.E.W.﹠amp; Strohmaier is among the K.G.; θ-1 zeolite is described in Nature, and 312,533-534 (1984) .Barri, S.A.I., Smith W.G., White, D and Young is among the D.; Mazzite is described in Microporous MesoporousMat., and 63,33-42 (2003), Martucci, A, Alberti, A, Guzmar-Castillo, M.D., Di Renzo, F and Fajula are among the F.; The L zeolite is described in Microporous Mesoporous Mat., and 76,81-99 (2004), Bhat, S.D., Niphadkair, P.S., Gaydharker, T.R., Awate, S.V., Belhekar, A.A.and Joshi among the P.N, also is described in J.Ind.Eng.Chem.Vol.10, No.4 (2004), 636-644, Ko Y.S is among the Ahn W.S, silicon potassium aluminium zeolite is described in Zeolites 255-264, and Vol.7 is among the 1987Howden M.G..
The zeolite catalyst that uses in the inventive method uses with the acid form, is commonly referred to ' H ' type zeolite, for example, the H-offretite.The zeolite of other form, for example NH
4The type zeolite can be converted into the H type, for example, and by at high temperature calcining NH
4Type.The acid zeolite has Bronsted acid (H
+) position, it is distributed in the various channel system of zeolite.For example, the H of H-offretite
+The position is arranged in 12 membered ring channels and 8 membered ring channels.Be arranged in the H of any special channel system
+The quantity of material or concentration can be determined for example infrared, NMR (Nuclear Magnetic Resonance) spectrum technology by prior art.Come quantitative Bronsted acidity by FTIR and NMR (Nuclear Magnetic Resonance) spectrum, for example, be described in Makarova; M.A., Wilson, A.E., van Liemt, BJ., Mesters, C.de Winter, A.W., Williams, C.Journal of Catalysis 1997,172, (1) is in 170.This duct of two types in the H-offretite (being limited with 8 yuan of rings by 12 yuan of rings) can produce at least two keys that link to each other with the hydroxyl zone of H-offretite, one corresponding to the vibration in the bigger hole, another with lower frequency vibration in less hole.The inventor's work shows the H that is arranged in 8 membered ring channels
+Have dependency between the quantity at position and the carbonylation speed, and do not observe this dependency for 12 membered ring channels.Have been found that the increase of carbonylation speed and H in 8 membered ring channels
+The quantity at position parallels.Comparatively speaking, there are not evidence demonstration and the H in 12 membered ring channels
+The dependency of the quantity at position.H in 8 membered ring channels
+The quantity at position can be passed through for example Na of metallic cation
+Or Co
2+Use known ion exchange technique to substitute H
+Control.
The chemical constitution of zeolite can be expressed as and relate to following molar relationship:
SiO
2∶X
2O
3
Wherein X is a trivalent element, for example aluminium, boron, iron and/or gallium, preferably aluminium.The SiO of given zeolite
2: X
2O
3Ratio is normally variable.For example, can synthesize as everyone knows and have SiO
2: Al
2O
3Than for 6-90 or bigger offretite, Y zeolite, it is about 6 to have about 1-, the about 2-2000 of chabazite, and can synthesize and have SiO
2: Al
2O
3Sarcolite greater than 4.Common SiO
2: X
2O
3The upper limit of ratio is unconfined, for example the ZSM-5 zeolite.The SiO of the zeolite that the present invention uses
2: X
2O
3Mol ratio is at least 5, preferred 7-40, for example 10-30.Preferred SiO
2: X
2O
3Mol ratio is less than or equal to 100.For many zeolites, special SiO
2: X
2O
3Than obtaining (wherein X is Al), by utilizing the standard technique of high-temperature steam processing or pickling by dealuminzation.
Depend on feed properties, water can produce on the spot.For example, when alcohol is used as charging, utilize pure dimerization reaction to ether to generate water, the esterification that water also can pass through alcohol and carboxylic acid product produces.Water can be introduced separately into or introduce with alcohol or ester feed component or its mixture.Water can exist with liquid state or gasiform form.Method of the present invention is carried out under aqueous conditions, and charging is when being Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ester, and the product of carbonylation reaction is corresponding carboxylic acid and/or ester.For example, when charging is methyl alcohol or ritalin, reaction product be acetic acid and/ritalin.In charging is C
1-C
3During alkyl oxide, dme for example, carbonylation reaction preferably carries out under anhydrous condition.Under anhydrous basically condition, the carbonylation selectivity of dme generates the ritalin product.
This is reflected at when implementing under the anhydrous basically condition, and catalyzer and preferred feed component should be carried out drying before beginning operation, for example, and by being preheating to 400-500 ℃.
Usually, be ether in charging, for example during dme, this method is equal to or less than under about 250 ℃ in temperature carries out, that is and, temperature is about 250 ℃ of about 100-, about 180 ℃ of preferably about 150-.When charging is alcohol or ester, for example methyl alcohol or ritalin, this method is carried out under greater than 250 ℃ temperature, and promptly temperature is about 400 ℃ of about 250-, about 350 ℃ of preferably about 275-.
Usually total working pressure is the about 100bar of about 1bar-, and the pressure that preferably has a carbon monoxide is lower than 5bar greater than the pressure of 10bar and reactant.
This method can be continuously or batch operation, usually preferred operate continuously.Basically, this method is operated in gas phase, and the reactant that is introduced into can be liquid state or gasiform, and product is as gas recovery.As requested, reaction product can be cooled and condensation subsequently.Catalyzer can use with suitable form, also can be with fixed bed or fluidized-bed.In the operation of this method, unreacted starting raw material can reclaim and be recycled in the reactor.When product is ritalin, can reclaims also and can former state sell, or as requested, can be transported in other chemical process unit.If desired, all reaction product can be sent into conversion and other optional component of being used for ritalin or acetic acid in the chemical process unit and be converted into other useful product.
In a preferred embodiment of the present invention, when product was ritalin, it can reclaim from reaction product and contact via hydrolysis reaction formation acetic acid with water.In addition, all products can pass through hydrolysing step, then and acetic acid separated.This hydrolysing step can carry out in the presence of acid catalyst, can adopt the mode of active distillation method known in the art.
After separation, any alcohol that obtains in reaction can be sent into and prepare ether in the dehydration reactor, and it can separate from water and be recycled in the carbonylation unit as the fresh feed of carbonylation reactor.
In another embodiment, in case when preparing a large amount of ester, then finish the hydrolysis of ester products to alcohol and carboxylic acid by on one or more points of catalyst bed, injecting water by carbonylation.Inject water with this mode and for example stopped dme basically, and eliminated the needs of the hydrolysis reactor that separates to this conversion of ritalin.
The following embodiment that provides is used to explain the present invention.Yet they have no intention to limit the scope of the invention.
General method
1) Preparation of catalysts
The catalyst sample of ammonia formula or acid utilizes Specac Press, compresses in the mould of 33mm with 12 tons pressure, crushes then and sieves into granularity grades 212-335 micron.Then, (in the furnace volume=30L), calcining is with NH in the still air normal atmosphere at retort furnace for this catalyzer (normally 1g)
4 +Form is converted into the H+ form.Temperature is raised to 450 ℃ with the soaring speed of 5 ℃/min from room temperature, keeps this temperature then 12 hours.The details of zeolite is described in the following table 1
Table 1
By in the 1 volumetric molar concentration ammonium nitrate solution of 10ml, stirring the 1g raw material three hours, filtering solution then, the zeolite A of na form is converted into NH
4 +Form.Repeat this operation three times, and before compressing and sieving, solid is dry down in 100 ℃ in air.NH before using
4 +The NaA of exchange is calcining not.
Dimethyl ether carbonylation reaction
Dimethyl ether carbonylation reaction is operated in the pressure current reactor unit that the parallel isothermal identical by 60 and flow tubular reactor are formed.In each pipe, with the 50ml catalyst cupport to having on the metal sintering thing that hole size is 20 μ m.All catalyst samples are with the soaring speed of 5 ℃/min, under atmospheric pressure, and at N
2In, flow velocity is 3.33ml/h, be heated to 100 ℃, and kept this temperature 1 hour.So this reactor is by N
2Be pressurized to 70barg, and this condition of this system held 1 hour.The nitrogen feed subsequent transformation is that gas flow rate is the mixture that contains 64mol% carbon monoxide, 16mol% hydrogen and 20mol% nitrogen of 3.33ml/h, and this system is heated to 300 ℃ with the soaring speed of 3 ℃/min.This condition of this system held is 3 hours then.After this, temperature is reduced to 180 ℃ and also stablized 10min.Think that at that point catalyst activation finishes, gas feed is converted into the mixture that contains 64mol% carbon monoxide, 16mol% hydrogen, 15mol% nitrogen and 5mol% dme that gas flow rate is 3.33ml/h.Reaction continues 27.8 hours, and temperature is elevated to 250 ℃ then.The materials flow of from reactor, coming out by have three pillars (molecular sieve 5A,
Q and CP-Wax-52), each pillar is furnished with Varian 4900 little gas chromatographs of thermal conductivity detector; And have two pillars (CP-Sil 5 and CP-Wax 52), each pillar is furnished with flame ionization detector, Interscience Trace gas chromatograph.The result of carbonylation reaction provides in table 2.
Table 2
| Embodiment | Catalyzer | Temperature of reaction/℃ | Time/hrs in the materials flow | STY MeOAcgl -1h -1 |
| 1. | NH4-silicon potassium aluminium zeolite-10 | 180 | 19.6 | 55 |
| 2. | 250 | 48.8 | 21 | |
| 3. | The NH4-chabazite | 180 | 19.7 | 13 |
| 4. | 250 | 49.0 | 0 | |
| 5. | NH4-ZSM-23 | 180 | 21.2 | 1 |
| 6. | 250 | 50.4 | 4 | |
| 7. | NH4-ECR-18 | 180 | 16.0 | 25 |
| 8. | 250 | 50.8 | 1 | |
| 9. | NH4-θ-1 | 180 | 17.3 | 0 |
| 10. | 250 | 52.1 | 1 | |
| 11. | Na-zeolite A | 180 | 21.4 | 0 |
| 12. | 250 | 50.6 | 0 | |
| 13. | The NH4-zeolite L | 180 | 20.3 | 0 |
| 14. | 250 | 49.5 | 0 | |
| 15. | The H-mazzite | 180 | 20.7 | 1 |
| 16. | 250 | 49.9 | 6 | |
| 17. | NH4-β-18 | 180 | 16.2 | 1 |
| 18. | 250 | 51.0 | 2 |
In above-mentioned test, the silicon-dioxide of silicon potassium aluminium zeolite, chabazite and ECR-18 zeolite: the window size that alumina molar ratio is at least 5,8 membered ring channels is at least 2.5
* at least 3.6
Have at least one Bronsted acidity position, and 8 membered ring channels interconnect with the duct that limits more than or equal to 8 yuan ring.These tests illustrate by these zeolites can obtain significant carbonylation activity.Yet, in carbonylation reaction, use zeolite, ZSM-23, θ-1, A zeolite, L zeolite, mazzite and β-18, almost do not find (if any) any carbonylation.ZSM-23, θ-1 only has 10 membered ring channels, do not have 8 membered ring channels; β-18 and L zeolite only have 12 membered ring channels, do not have 8 membered ring channels; The A zeolite has 8 membered ring channels but the ratio of its silica/alumina is lower than 5; Existing 8 membered ring channels of mazzite also have 12 membered ring channels, but 8 membered ring channels do not interconnect with 8 membered ring channels or 12 membered ring channels.
General method B
In order to study the catalytic activity that the methanol carbonyl that is used to not have iodide changes into the zeolite of acetic acid, this zeolite can be tested in band baric flow reactor according to following program.With size is that the zeolite pellets of 500-1000um is loaded in the band baric flow reactor.Also use the catalyzer external crucible to guarantee the effective mixing/heating of reactant.External crucible is to make methyl alcohol form methyl alcohol/dme/isorrheic gama-alumina.By at nitrogen gas stream (100cm
3/ min) in, kept 16 hours down in 350 ℃, then at carbon monoxide (200cm
3/ min) in, kept 2 hours down in 350 ℃, make this catalyst activation.Utilize back pressure regulator that this system is pressurized to 30barg then.The flow velocity of carbon monoxide is adjusted to 400cm
3/ min (GHSV=2200), methyl alcohol is introduced in this reactor (speed+0.15ml/min) via pump.Liquid product and unconverted reactant are collected in the cold collector, and gaseous product and unreacted feed utilize on-line gas chromatograph to take a sample in the downstream.This reaction is by frequent interval sampling, and liquid product utilizes gas-chromatography to carry out off-line analysis.In above-mentioned carbonylation of methanol, use zeolite H-offretite (silicon-dioxide: alumina molar ratio is 10) as catalyzer, expect that a large amount of ritalins and acetic acid all become liquid product.Similarly be, to expect that a large amount of ritalins and acetic acid all become liquid product if use zeolite H-sarcolite (silicon-dioxide: alumina molar ratio is 8) as the catalyzer of above-mentioned carbonylation of methanol.Offretite and sarcolite all have and interconnective 8 membered ring channels of 12 membered ring channels.Comparatively speaking, (silicon-dioxide: alumina molar ratio is 23 if zeolite H-ZSM-5 is used in expection; 10 membered ring channels are only arranged) or zeolite H-Y (silicon-dioxide: alumina molar ratio is 12; 12 membered ring channels are only arranged) as catalyzer, only there is the acetic acid of trace can become liquid product.
All publications and the patent application of quoting in this manual are hereby incorporated by, just as each independent publication or patent application by clear and definite and point out to be incorporated herein by reference separately.
Although in order clearly to understand goal of the invention, foregoing invention is by setting forth and embodiment has carried out some detailed descriptions, however those do not break away from according to instruction of the present invention claims spirit or scope some variation and revise apparent to those skilled in the art.
Claims (42)
1. one kind prepares C
1-C
3The method of aliphatic carboxylic acid and/or corresponding esters is by with corresponding C
1-C
3Fatty Alcohol(C12-C14 and C12-C18) and/or its ester or ether derivant and carbon monoxide carbonylation in the presence of the catalyzer that contains zeolite with at least one 8 membered ring channel, described 8 membered ring channels with interconnect by the duct that ring limited more than or equal to 8 yuan, described 8 yuan of rings have at least
* at least
Window size and at least one Bronsted acid position, and the silicon-dioxide of zeolite: X
2O
3Mol ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
2. according to the process of claim 1 wherein C
1-C
3Carboxylic acid is an acetic acid.
3. according to the process of claim 1 wherein C
1-C
3The ester of carboxylic acid is a ritalin.
4. according to the process of claim 1 wherein C
1-C
3Alcohol is methyl alcohol or ethanol.
5. according to the method for claim 4, wherein alcohol is methyl alcohol.
6. according to the process of claim 1 wherein that ether is by carbonylation.
7. according to the method for claim 6, wherein ether is dme.
According to the process of claim 1 wherein ether under about 100 ℃-Yue 250 ℃ by carbonylation.
According to the process of claim 1 wherein ether under about 150 ℃-Yue 180 ℃ by carbonylation.
10. according to Claim 8 or 9 method, wherein ether is dme.
11. according to the process of claim 1 wherein alcohol or its ester derivative under about 250 ℃-Yue 400 ℃ by carbonylation.
12. according to the process of claim 1 wherein alcohol or its ester derivative under about 275 ℃-Yue 350 ℃ by carbonylation.
13. according to the method for claim 11 or 12, wherein alcohol is methyl alcohol, and ester derivative is a ritalin.
14. according to the process of claim 1 wherein that catalyzer comprises fixed bed catalyst.
15. according to the process of claim 1 wherein that catalyzer comprises fluid catalyst.
16. continuation method according to claim 1.
17. batch process according to claim 1.
18. according to the process of claim 1 wherein that the charging that contains carbon monoxide further comprises hydrogen.
19. according to the method for claim 18, the charging that wherein contains carbon monoxide comprises synthetic gas.
20. according to the process of claim 1 wherein that the derivative of alcohol is C
1-C
3Ether, and this method carries out under anhydrous basically condition, and product is corresponding ester.
21. according to the method for claim 20, wherein ether is dme, and this method carries out under anhydrous basically condition, product is a ritalin.
22., comprise that further ester hydrolysis is with the preparation corresponding carboxylic acid according to the method for claim 20.
23., comprise that further hydrolysis ritalin is with preparation acetic acid according to the method for claim 21.
24. according to the method for claim 22 or 23, wherein hydrolysis is implemented in the reactor that separates with the ester preparation feedback.
25. according to the method for claim 22 or 23, wherein hydrolysis is implemented in the reactor identical with the ester preparation feedback.
26. according to the process of claim 1 wherein that zeolite catalyst is selected from the zeolite that framework types is OFF, CHA, ITE, GME, ETR, EON and MFS.
27. according to the method for claim 26, wherein catalyzer is selected from offretite, sarcolite, ZSM-57 and ECR-18.
28. according to the method for claim 27, its mesolite is an offretite.
29. according to the process of claim 1 wherein that catalyzer is by only being made up of the duct of 8 yuan of ring qualifications.
30. interconnect by having the duct that limits greater than 8 yuan ring by 8 yuan of ducts of limiting of ring and at least one according to the process of claim 1 wherein.
31. according to the method for claim 30, wherein, at least one is limited by 10 or 12 yuan of rings by the duct that limits greater than 8 yuan ring.
32. according to the method for claim 31, wherein, at least one is limited by 12 yuan of rings by the duct that limits greater than 8 yuan ring.
33. according to the process of claim 1 wherein that this method carries out under aqueous conditions.
34. according to the method for claim 33, wherein water is introduced separately, or is introduced into alcohol and/or its ester.
35. according to the process of claim 1 wherein silicon-dioxide: X
2O
3Ratio be less than or equal to 100.
36. according to the process of claim 1 wherein silicon-dioxide: X
2O
3Ratio be 7-40.
37. according to the process of claim 1 wherein silicon-dioxide: X
2O
3Ratio be 10-30.
38. according to the process of claim 1 wherein that X is selected from aluminium, gallium and its mixture.
39. according to the process of claim 1 wherein that X is an aluminium.
40. according to the process of claim 1 wherein that X is an aluminium, and silicon-dioxide: Al
2O
3Ratio be less than or equal to 100.
41. according to the method for claim 40, wherein silicon-dioxide: Al
2O
3Ratio be 7-40.
42. according to the method for claim 40, wherein silicon-dioxide: Al
2O
3Ratio be 10-30.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2006/047718 WO2008073096A1 (en) | 2006-12-15 | 2006-12-15 | Process for carbonylation of aliphatic alcohols and/or reactive derivatives thereof |
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|---|---|
| CN101600678A true CN101600678A (en) | 2009-12-09 |
| CN101600678B CN101600678B (en) | 2012-08-15 |
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ID=39512001
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|---|---|---|---|
| CN2006800566291A Expired - Fee Related CN101600678B (en) | 2006-12-15 | 2006-12-15 | Process for carbonylation of aliphatic alcohols and/or reactive derivatives thereof |
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| Country | Link |
|---|---|
| EP (1) | EP2114850A4 (en) |
| JP (1) | JP2010513270A (en) |
| KR (2) | KR20140054448A (en) |
| CN (1) | CN101600678B (en) |
| BR (1) | BRPI0622186A2 (en) |
| CA (1) | CA2671361C (en) |
| UA (1) | UA95663C2 (en) |
| WO (1) | WO2008073096A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012062A (en) * | 2012-12-20 | 2013-04-03 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN105358521A (en) * | 2013-03-08 | 2016-02-24 | 英国石油化学品有限公司 | Carbonylation process |
| WO2017012244A1 (en) * | 2015-07-20 | 2017-01-26 | 中国科学院大连化学物理研究所 | Lower fatty carboxylic acid alkyl ester production method |
| WO2017012246A1 (en) * | 2015-07-20 | 2017-01-26 | 中国科学院大连化学物理研究所 | Methyl acetate preparation method |
| CN111511709A (en) * | 2017-08-24 | 2020-08-07 | 英国石油有限公司 | Method of producing a composite material |
| CN114539057A (en) * | 2020-11-18 | 2022-05-27 | 中国科学院大连化学物理研究所 | Preparation method of methyl acetate |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2292578A1 (en) * | 2009-09-03 | 2011-03-09 | BP Chemicals Limited | Process for producing acetic acid and dimethyl ether using a zeolite catalyst |
| CN106365992B (en) * | 2015-07-20 | 2019-01-01 | 中国科学院大连化学物理研究所 | A method of preparing acetal carbonyl compound |
| WO2019037768A1 (en) | 2017-08-24 | 2019-02-28 | Bp P.L.C. | Process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3130007A (en) | 1961-05-12 | 1964-04-21 | Union Carbide Corp | Crystalline zeolite y |
| GB1185453A (en) | 1967-02-20 | 1970-03-25 | Monsanto Co | Multiphase Catalysis. |
| US3717670A (en) | 1968-08-02 | 1973-02-20 | Monsanto Co | Production of carboxylic acids and esters |
| US3689533A (en) | 1971-03-15 | 1972-09-05 | Monsanto Co | Production of carboxylic acids and esters |
| CA1064890A (en) | 1975-06-10 | 1979-10-23 | Mae K. Rubin | Crystalline zeolite, synthesis and use thereof |
| US4612387A (en) * | 1982-01-04 | 1986-09-16 | Air Products And Chemicals, Inc. | Production of carboxylic acids and esters |
| GB9223170D0 (en) | 1992-11-05 | 1992-12-16 | British Petroleum Co Plc | Process for preparing carboxylic acids |
| CA2159410A1 (en) | 1994-11-14 | 1996-05-15 | Pei-Shing Eugene Dai | Catalyst for multistage etherification with high conversion of t-butanol |
| US6127432A (en) * | 1998-01-29 | 2000-10-03 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for preparing oxygenates and catalysts therefor |
| GB0409490D0 (en) * | 2004-04-28 | 2004-06-02 | Bp Chem Int Ltd | Process |
| US20060252959A1 (en) * | 2005-05-05 | 2006-11-09 | The Regents Of The University Of California | Process for carbonylation of alkyl ethers |
-
2006
- 2006-12-15 EP EP06845427A patent/EP2114850A4/en not_active Withdrawn
- 2006-12-15 KR KR1020147009999A patent/KR20140054448A/en not_active Application Discontinuation
- 2006-12-15 CN CN2006800566291A patent/CN101600678B/en not_active Expired - Fee Related
- 2006-12-15 BR BRPI0622186-6A patent/BRPI0622186A2/en not_active IP Right Cessation
- 2006-12-15 JP JP2009541278A patent/JP2010513270A/en active Pending
- 2006-12-15 KR KR1020097012298A patent/KR20090092280A/en active Application Filing
- 2006-12-15 CA CA2671361A patent/CA2671361C/en not_active Expired - Fee Related
- 2006-12-15 WO PCT/US2006/047718 patent/WO2008073096A1/en active Application Filing
- 2006-12-15 UA UAA200907279A patent/UA95663C2/en unknown
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012062B (en) * | 2012-12-20 | 2015-04-22 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN103012062A (en) * | 2012-12-20 | 2013-04-03 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN105358521B (en) * | 2013-03-08 | 2018-12-21 | 英国石油化学品有限公司 | carbonylation method |
| CN105358521A (en) * | 2013-03-08 | 2016-02-24 | 英国石油化学品有限公司 | Carbonylation process |
| WO2017012244A1 (en) * | 2015-07-20 | 2017-01-26 | 中国科学院大连化学物理研究所 | Lower fatty carboxylic acid alkyl ester production method |
| CN106365994A (en) * | 2015-07-20 | 2017-02-01 | 中国科学院大连化学物理研究所 | Lower aliphatic carboxylic acid alkyl ester production method |
| WO2017012246A1 (en) * | 2015-07-20 | 2017-01-26 | 中国科学院大连化学物理研究所 | Methyl acetate preparation method |
| CN106365994B (en) * | 2015-07-20 | 2019-01-01 | 中国科学院大连化学物理研究所 | A kind of production method of lower aliphatic carboxylic acid's Arrcostab |
| EA032939B1 (en) * | 2015-07-20 | 2019-08-30 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайэнс | Methyl acetate preparation method |
| EA035233B1 (en) * | 2015-07-20 | 2020-05-19 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайэнс | Lower fatty acid alkyl ester production method |
| CN111511709A (en) * | 2017-08-24 | 2020-08-07 | 英国石油有限公司 | Method of producing a composite material |
| US11427524B2 (en) | 2017-08-24 | 2022-08-30 | Bp P.L.C. | Process for dehydrating methanol to dimethyl ether product |
| CN111511709B (en) * | 2017-08-24 | 2023-05-30 | 英国石油有限公司 | Methanol dehydration method |
| CN114539057A (en) * | 2020-11-18 | 2022-05-27 | 中国科学院大连化学物理研究所 | Preparation method of methyl acetate |
| CN114539057B (en) * | 2020-11-18 | 2024-03-19 | 中国科学院大连化学物理研究所 | Preparation method of methyl acetate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010513270A (en) | 2010-04-30 |
| CA2671361A1 (en) | 2008-06-19 |
| CN101600678B (en) | 2012-08-15 |
| CA2671361C (en) | 2014-10-21 |
| EP2114850A1 (en) | 2009-11-11 |
| UA95663C2 (en) | 2011-08-25 |
| KR20140054448A (en) | 2014-05-08 |
| KR20090092280A (en) | 2009-08-31 |
| BRPI0622186A2 (en) | 2011-12-27 |
| EP2114850A4 (en) | 2013-03-27 |
| WO2008073096A1 (en) | 2008-06-19 |
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