WO2005028417A1 - Verfahren zur herstellung von xylylendiamin (xda) - Google Patents
Verfahren zur herstellung von xylylendiamin (xda) Download PDFInfo
- Publication number
- WO2005028417A1 WO2005028417A1 PCT/EP2004/009568 EP2004009568W WO2005028417A1 WO 2005028417 A1 WO2005028417 A1 WO 2005028417A1 EP 2004009568 W EP2004009568 W EP 2004009568W WO 2005028417 A1 WO2005028417 A1 WO 2005028417A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- quench
- hydrogenation
- phthalonitrile
- nmp
- xylylenediamine
- Prior art date
Links
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000010791 quenching Methods 0.000 claims abstract description 66
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 32
- 238000009835 boiling Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008096 xylene Substances 0.000 claims description 12
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 239000002904 solvent Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 description 10
- 230000000171 quenching effect Effects 0.000 description 10
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CJAAPVQEZPAQNI-UHFFFAOYSA-N (2-methylphenyl)methanamine Chemical compound CC1=CC=CC=C1CN CJAAPVQEZPAQNI-UHFFFAOYSA-N 0.000 description 3
- RGXUCUWVGKLACF-UHFFFAOYSA-N (3-methylphenyl)methanamine Chemical compound CC1=CC=CC(CN)=C1 RGXUCUWVGKLACF-UHFFFAOYSA-N 0.000 description 3
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011552 falling film Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- -1 nitrile compounds Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004514 thermodynamic simulation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001717 carbocyclic compounds Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
Definitions
- the present invention relates to a method for producing xylylenediamine comprising the steps
- Xylylenediamine bis (aminomethyl) benzene
- Xylylenediamine is a useful starting material, e.g. for the synthesis of polyamides, epoxy hardeners or as an intermediate for the production of isocyanates.
- xylylenediamine encompasses the three isomers ortho-xylylenediamine, meta-xylylenediamine (MXDA) and para-xylylenediamine.
- EP-A2-1 113001 (Mitsubishi Gas Chem. Comp.) Describes a process for the production of nitrile compounds by ammoxidation of corresponding carbocyclic or heterocyclic compounds, excess ammonia being recycled from the reaction product. Also described is the direct contacting of the vaporous product of the ammoxidation step with a liquid organic solvent, which is in particular aliphatic or aromatic hydrocarbons. (Paragraphs [0045] and [0046]).
- EP-A2-1 193247 and EP-A1-1 279 661 (both Mitsubishi Gas Chem. Comp.) Relate to a process for the purification of isophthalonitrile (IPDN) and a process for the production of pure XDA, in which the phthalonitrile by ammoxidation of Xylene is synthesized, the vaporous product of the ammoxidation stage being brought directly into contact with a liquid organic solvent (quench).
- IPDN isophthalonitrile
- XDA isophthalonitrile by ammoxidation of Xylene
- the organic solvent is selected from alkylbenzenes, heterocyclic compounds, aromatic nitriles and heterocyclic nitriles and has a boiling point below that of phthalonitrile (EP-A2-1 193247: column 4, paragraphs [0018] and [0019]; EP -A1-1 279 661: columns 4-5, paragraph [0023] and [0024]).
- EP-A2-1 193244 Mitsubishi Gas Chem.
- Preferred organic solvents are C 6 -C 2 aromatic hydrocarbons, such as xylene and pseudocumene (column 6, paragraph [0027] and [0028]).
- the object of the present invention was to find an improved economical process for the preparation of high-purity xylylenediamine, in particular meta-xylylenediamine, with a high yield and space-time yield (RZA), which can be achieved using processes of the prior art (for example EP A2-1 193244) enables comparable throughputs due to reduced material flows, in particular solvent flows, including recycle streams, reduced apparatus and machines.
- RZA space-time yield
- the process according to the invention is preferably used for the preparation of meta-xylylenediamine (MXDA) by hydrogenation of isophthalonitrile (IPDN), which is synthesized in a previous step by ammoxidation of meta-xylene.
- MXDA meta-xylylenediamine
- IPDN isophthalonitrile
- the method according to the invention can be carried out as follows: Ammoxidation stage:
- ammoxidation of xylene (o-, m- or p-xylene) to the corresponding phthalonitrile (ortho-xylene ->o-phthalonitrile; meta-xylene • isophthalonitrile; para-xylene - terephthalodinitrile) is generally carried out by methods known to those skilled in the art carried out.
- the ammoxidation of the methyl aromatic is preferably carried out on a multi-oxide catalyst with ammonia and an oxygen-containing gas (oxygen or air or both) in a fluidized bed reactor or a tube (bundle).
- the reaction temperature is generally 300 to 500 ° C, preferably 330 to 480 ° C.
- the catalyst preferably contains V, Sb and / or Cr and is particularly preferably composed of [V, Sb and alkali metals] or [V, Cr, Mo and B], in each case as a full catalyst or on an inert support.
- SiO 2 , Al 2 O 3 or a mixture of the two or steatite are preferred as inert carriers.
- ammoxidation can also be carried out according to the processes described in the applications EP-A2-1 113 001, EP-A2-1 193 247, EP-A1-1 279 661 and EP-A2-1 193 244.
- NMP N-methyl-2-pyrrolidone
- the NMP used for the quench can also contain already dissolved or suspended phthalonitrile (preferably the isomer that corresponds to the synthesized PDN).
- the vaporous phthalonitrile is absorbed directly into the liquid solvent NMP by the quench, a solution and / or a suspension being formed which can be further processed immediately.
- NMP with a purity> 99% by weight, in particular> 99.5% by weight is generally used as the fresh feed.
- NMP recovered from the process can preferably be used as the quench liquid.
- the purity of the quench liquid can also be ⁇ 99% by weight, e.g. 90-98% by weight, especially if they are not extraneous to the process (i.e. water, ammonia, benzonitrile, tolunitrile, xylene, o-, m- or p-methylbenzylamine, benzylamine, xylylenediamine) acts as impurities.
- the amount of solvent NMP used is generally such that solutions / suspensions with a phthalonitrile content of 15 to 75% by weight, preferably 25 to 60% by weight, are obtained.
- the vapor discharge of the ammoxidation containing the phthalonitrile (PDN) is introduced into the liquid NMP in a quench apparatus, e.g. preferably in a falling film condenser (thin film, falling film or falling flow condenser), in a nozzle apparatus or in a column.
- a quench apparatus e.g. preferably in a falling film condenser (thin film, falling film or falling flow condenser), in a nozzle apparatus or in a column.
- the vaporous phthalonitrile can be carried out in cocurrent or in countercurrent with the liquid solvent.
- the vaporous phthalonitrile is introduced into the quench apparatus from above.
- the tangential supply of the liquid solvent at the top of the falling film condenser or the supply of the liquid solvent through one or more nozzles is advantageous in order to achieve complete wetting of the inner wall of the quench apparatus.
- the gas from the ammoxidation is introduced at the bottom of the column and the solvent is fed in at the top.
- the quench apparatus can be equipped with internals such as floors, ordered packings or unordered fillings.
- the NMP for the quench can be used in a single pass or as a circulating medium.
- Part of the quench solution or suspension is advantageously circulated.
- the quench solution or suspension is cooled by means of a heat exchanger installed in the circuit.
- the temperature of the circulating medium and the circulating volume flow are set and matched to one another so that the desired temperature is reached in the quench outlet.
- the temperature of the circulating medium is chosen to be lower, the smaller the volume flow of the circulating medium and vice versa, taking into account solubilities and melting points as well as the hydraulic loading limits of the quenching apparatus.
- the volume flow of the freshly flowing NMP depends on the quench temperature, since the higher the temperature, the more solvent is contained in the vaporous quench discharge. It is set so that the desired concentration of the PDN solution or suspension is obtained. Since the solubility of PDN in NMP increases with increasing temperature, a higher PDN concentration in the NMP can be achieved with increasing quench outlet temperature.
- the circulating medium is fed in together with the fresh solvent or separately from it at a suitable point in the quench apparatus.
- the fresh NMP is fed in at the top and the circulating medium further down, for example in the middle of the column.
- the temperature of the liquid quench discharge is adjusted to 40 to 180 ° C., preferably 50 to 120 ° C., in particular 80 to 120 ° C., by tempering the NMP and / or the circulating medium.
- the boiling point of phthalonitrile is in the range of 1 to 100 mbar, about 60 Kelvin above the boiling point of NMP.
- the absolute pressure during quenching is generally 0.5 to 1.5 bar. Driving is preferably carried out at a slight excess pressure.
- Xylene, water, NH 3 , CO 2 , N 2 etc., which are usually contained in the vaporous discharge of the ammoxidation, are only partially or practically not dissolved under quench conditions in the quench solvent NMP and are predominantly gaseous from the quench apparatus separated.
- PDN at the same pressure
- Suspension water and possibly products with a boiling point lower than phthalonitrile (at the same pressure) low boilers; e.g. unreacted xylene, benzo nitrile, tolunitrile, each as a heteroazeotrope with water, water, benzonitrile, tolunitrile; Enumeration with increasing boiling point (at the same pressure); such as optionally also o-, m- or p-methyl-benzylamine, benzylamine, xylylenediamine, these amines originating from recycled solvents from the hydrogenation stage) being removed partially or completely by distillation.
- low boilers e.g. unreacted xylene, benzo nitrile, tolunitrile, each as a heteroazeotrope with water, water, benzonitrile, tolunitrile; Enumeration with increasing boiling point (at the same pressure); such as optionally also o-, m- or p-methyl-benzylamine, benzylamine
- This removal of the low boilers is preferably carried out overhead in a distillation column.
- a distillation column is preferably used, which is preferably equipped with the usual internals for increasing the separation capacity, such as trays, ordered or unordered packings, etc.
- the design of the column (in particular the number of separation stages, feed point, reflux ratio, etc.) can be carried out by the person skilled in the art according to methods which are familiar to the particular composition of the solution or suspension.
- the quench solution or suspension obtained is then fed to the hydrogenation.
- NMP or another organic solvent such as e.g. Xylene, benzylamine, o-, m- or p-methylbenzylamine, xylylenediamine and mixtures thereof can be added.
- the phthalonitrile obtained as an intermediate is not isolated in substance.
- the phthalonitrile to be hydrogenated is not separated from the NMP used in the quenching step for the hydrogenation stage.
- a separation of high boilers, that is to say products having a boiling point higher than phthalonitrile (at the same pressure), from the quench solution or suspension preferably does not take place in the process according to the invention.
- ammonia preferably in liquid form, is particularly preferably added to the solution or suspension.
- the ammonia can be added directly after the quench stage or only in the hydrogenation stage.
- the weight ratio of dinitrile to ammonia in the fresh feed is generally 1: 0.15 to 1:15, preferably 1: 0.5 to 1:10, particularly preferably 1: 1 to 1: 5.
- the catalysts and reactors known to those skilled in the art for this reaction e.g. fixed bed or suspension procedure
- processes continuous, semi-continuous, discontinuous
- the hydrogenation reactor can be operated in a single pass. Alternatively, a cycle procedure is also possible in which a part of the reactor discharge is returned to the reactor inlet, preferably without the circuit stream having to be worked up beforehand.
- the circuit stream can be cooled in a simple and inexpensive manner by means of an external heat exchanger, and the heat of reaction can thus be removed.
- the reactor can also be operated adiabatically, the temperature rise in the reaction solution being able to be limited by the cooled circuit stream. Since the reactor does not have to be cooled even then, a simple and inexpensive design is possible.
- An alternative is a cooled tube bundle reactor.
- Catalysts which contain cobalt and / or nickel and / or iron, as a full catalyst or on an inert support, are preferred.
- the reaction temperatures are generally 40 to 150 ° C, preferably 40 to 120 ° C.
- the pressure is generally 40 to 300 bar, preferably 100 to 200 bar.
- the xylylenediamine is preferably purified by distilling off low-boiling secondary products (at the same pressure) overhead and distillative removal of high-boiling impurities via the bottom.
- the low-boiling and heavy-boiling by-products can also be separated off in a side draw or dividing wall column, pure xylylenediamine being obtained via a liquid or gaseous side draw.
- the product (XDA) is additionally extracted with an organic solvent, preferably an aliphatic hydrocarbon, in particular a cycloaliphatic hydrocarbon, very particularly cyclohexane or methylcyclohexane.
- an organic solvent preferably an aliphatic hydrocarbon, in particular a cycloaliphatic hydrocarbon, very particularly cyclohexane or methylcyclohexane.
- Figure 1 in the system provides a schematic overview of a preferred embodiment of the method according to the invention.
- the optional process steps “Water separation” and “Extractive XDA cleaning” are shown in dashed lines.
- a catalyst of the composition V 4 Sb 3 Wo l Cs 0 ⁇ 2 on steatite was installed as a fixed bed in a tubular reactor.
- the apparatus was heated from the outside to 400 ° C.
- the front part of the reactor was filled with an inert bed so that the feedstocks premixed and preheated to 400 ° C. reached the reaction zone. There was a slight excess pressure of 0.02-0.03 bar in the reactor.
- the hot spot temperature reached 450 ° C. With a conversion (U) of m-xylene of 79%, a selectivity (S) to IPDN of 68% was obtained.
- the gas mixture emerging from the reactor is quenched in a column with NMP.
- a solution of IPDN in NMP which contains 0.6% by weight of m-xylene, 1.6% by weight of water, 0.1% by weight of benzonitrile, 4% by weight, is discharged from the quench column at 122 ° C. % Tolunitrile, 27 wt .-% IPDN and about 66.7 wt .-% NMP contains. Unreacted reaction gases and inert gases as well as unreacted m-xylene and some NMP are drawn off in gaseous form at the top of the quench column.
- This gas can be worked up in order to return the valuable substances (in particular NH 3 , m-xylene, NMP and tolunitrile) to the reaction stage or the quench circuit.
- valuable substances in particular NH 3 , m-xylene, NMP and tolunitrile
- Inert and accompanying components H 2 O, benzonitrile, N 2 , CO 2 , etc. are removed from the processing stage.
- the hydrogenation was carried out in the presence of H 2 and 5 g of Raney nickel catalyst at 100 ° C. and a pressure of 100 bar in a stirred autoclave.
- IPDN The conversion of IPDN was quantitative, a yield of 92% based on the IPDN used being obtained.
- the data given above for the quench step are the results of a thermodynamic simulation.
- the quench was calculated as an apparatus in which there is a thermodynamic equilibrium between the gas and liquid phases.
- real binary data were used in the calculation Calculations can be carried out using commercial computer programs, here: Aspen Plus, which are familiar to the person skilled in the art).
- the ammoxidation was carried out as in Example 1, but the exit temperature from the quench is 91 ° C.
- the water content of the solution is 5.2% by weight.
- the solution is fed to a column with 15 bubble-cap trays. The inlet is on the 6th bell bottom.
- the water is removed overhead together with other components (dissolved gases, m-xylene, benzonitrile, tolunitrile, the latter as azeotropes with water).
- a practically water-free solution consisting of approximately 27% by weight IPDN, 67% by weight NMP, 6% by weight tolunitrile and 600% by weight benzonitrile is obtained via the bottom.
- a catalyst of the composition V 4 Sb 3 Ko l Ba 0 , 2 on steatite was installed as a fixed bed in a tubular reactor.
- the apparatus was heated from the outside to 415 ° C.
- the catalyst of the first half of the reactor was diluted with 70% by weight of steatite balls, the second half with 40% by weight. There was a slight overpressure of 0.02 bar in the reactor.
- the hot spot temperature reached 430 ° C. With a conversion of m-xylene of 88%, a selectivity to IPDN of 71% was obtained.
- the gas mixture emerging from the reactor is quenched in a column with NMP.
- a solution of IPDN in NMP which contains 0.25% by weight of m-xylene, 1.3% by weight of water, is discharged from the quench column at 120 ° C. and 1.02 bar (abs.)
- IPDN in NMP The solubility of IPDN in NMP is approx. 26% by weight at 60 ° C and approx. 41% by weight at 90 ° C. At 90 ° C, pseudocumene only has a solubility of 20% by weight and mesitylene only 12% by weight.
- the solubility of IPDN in mesitylene or pseudocumene is in each case less than 10% by weight.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/571,584 US7541497B2 (en) | 2003-09-10 | 2004-08-27 | Method for producing xylylenediamine (XDA) |
EP04764542A EP1663942B1 (de) | 2003-09-10 | 2004-08-27 | Verfahren zur herstellung von meta-xylylendiamin (mxda) |
JP2006525686A JP4488527B2 (ja) | 2003-09-10 | 2004-08-27 | キシリレンジアミン(xda)の製造法 |
DE502004003420T DE502004003420D1 (de) | 2003-09-10 | 2004-08-27 | Verfahren zur herstellung von meta-xylylendiamin (mxda) |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10341613.7 | 2003-09-10 | ||
DE10341613A DE10341613A1 (de) | 2003-09-10 | 2003-09-10 | Verfahren zur Herstellung von Xylylendiamin |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005028417A1 true WO2005028417A1 (de) | 2005-03-31 |
Family
ID=34305632
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/009568 WO2005028417A1 (de) | 2003-09-10 | 2004-08-27 | Verfahren zur herstellung von xylylendiamin (xda) |
Country Status (7)
Country | Link |
---|---|
US (1) | US7541497B2 (de) |
EP (1) | EP1663942B1 (de) |
JP (1) | JP4488527B2 (de) |
CN (1) | CN100361960C (de) |
AT (1) | ATE358665T1 (de) |
DE (2) | DE10341613A1 (de) |
WO (1) | WO2005028417A1 (de) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007088131A3 (de) * | 2006-02-01 | 2007-10-04 | Basf Ag | Verfahren zur herstellung von reinem xylylendiamin (xda) |
US7323598B2 (en) | 2003-09-10 | 2008-01-29 | Basf Aktiengesellschaft | Preparation of xylylenediamine (XDA) |
US7368610B2 (en) | 2003-09-10 | 2008-05-06 | Basf Aktiengesellschaft | Preparation of xylylenediamine (XDA) |
US7528284B2 (en) | 2003-09-10 | 2009-05-05 | Basf Aktiengesellschaft | Method for producing xylylenediamine (XDA) |
US7541497B2 (en) | 2003-09-10 | 2009-06-02 | Basf Aktiengesellschaft | Method for producing xylylenediamine (XDA) |
US7728174B2 (en) | 2005-08-02 | 2010-06-01 | Basf Se | Continuous hydrogenation processes for the preparation of xylylenediamines |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005026099A1 (de) | 2003-09-10 | 2005-03-24 | Basf Aktiengesellschaft | Verfahren zur herstellung von xylylendiamin durch kontinuierliche hydrierung von flüssigem phthalodinitril |
DE102005003315A1 (de) * | 2005-01-24 | 2006-08-03 | Basf Ag | Verfahren zur Herstellung eines Xylylendiamins |
DE102005045806A1 (de) * | 2005-09-24 | 2007-03-29 | Basf Ag | Verfahren zur Herstellung von Xylylendiamin |
CN101432067A (zh) * | 2006-04-28 | 2009-05-13 | 巴斯夫欧洲公司 | 用于氨氧化的新型负载型催化剂 |
US8212080B2 (en) * | 2008-12-26 | 2012-07-03 | Mitsubishi Gas Chemical Company, Inc. | Production method of xylylenediamine |
US9024070B2 (en) | 2011-01-31 | 2015-05-05 | Mitsubishi Gas Chemical Company, Inc. | Method for producing xylylenediamine |
JP2013177346A (ja) * | 2012-02-28 | 2013-09-09 | Mitsubishi Gas Chemical Co Inc | メタキシリレンジアミンの製造方法 |
JP2013177345A (ja) * | 2012-02-28 | 2013-09-09 | Mitsubishi Gas Chemical Co Inc | キシリレンジアミンの製造方法 |
CN109456200B (zh) * | 2018-11-23 | 2021-07-23 | 万华化学集团股份有限公司 | 一种间苯二甲胺的制备方法 |
CN113365975A (zh) * | 2019-03-20 | 2021-09-07 | 三菱瓦斯化学株式会社 | 苯二甲胺的制造方法 |
CN113429314A (zh) * | 2021-06-22 | 2021-09-24 | 四川金象赛瑞化工股份有限公司 | 一种硝酸铵和苯二甲胺联产方法及换热网络 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2970170A (en) * | 1957-03-22 | 1961-01-31 | California Research Corp | Preparation of xylylenediamines |
GB1164354A (en) * | 1966-07-04 | 1969-09-17 | Toyo Rayon Co Ltd | Process for the Hydrogenation of Nitriles. |
EP1193244A2 (de) * | 2000-09-25 | 2002-04-03 | Mitsubishi Gas Chemical Company, Inc. | Verfahren zur Herstellung von Xylylendiamin |
EP1209146A1 (de) * | 2000-11-16 | 2002-05-29 | Basf Aktiengesellschaft | Verfahren zur Hydrierung von Nitrilen zu primären Aminen an Raney-Katalysatoren |
EP1279661A1 (de) * | 2001-07-16 | 2003-01-29 | Mitsubishi Gas Chemical Company, Inc. | Verfahren zur Herstellung von hochreinem Xylylendiamin |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS517659B1 (de) | 1970-12-24 | 1976-03-10 | ||
AT324352B (de) * | 1972-10-05 | 1975-08-25 | Studiengesellschaft Kohle Mbh | Verfahren zur herstellung von organischen metallverbindungen durch elektrochemische umsetzung von metallen und h-aciden verbindungen |
DE60040720D1 (de) | 1999-12-27 | 2008-12-18 | Mitsubishi Gas Chemical Co | Verfahren zur Herstellung von Nitrilverbindungen |
DE60129907T2 (de) | 2000-09-21 | 2007-12-06 | Mitsubishi Gas Chemical Co., Inc. | Verfahren zur Reinigung von Isophthalonitril |
JP5017755B2 (ja) | 2001-07-16 | 2012-09-05 | 三菱瓦斯化学株式会社 | 高純度キシリレンジアミンの製造方法 |
US7161021B2 (en) | 2001-12-13 | 2007-01-09 | Mitsubishi Gas Chemical Company, Inc. | Process for producing a polynitrile compound |
US20030114702A1 (en) | 2001-12-13 | 2003-06-19 | Kenichi Nakamura | Process for producing a nitrile compound |
JP4240191B2 (ja) | 2002-03-11 | 2009-03-18 | 三菱瓦斯化学株式会社 | 芳香族ニトリルおよび複素環ニトリルの製造方法 |
JP4304420B2 (ja) | 2002-07-01 | 2009-07-29 | 三菱瓦斯化学株式会社 | キシリレンジアミンおよび/またはシアノベンジルアミンの製造方法 |
DE10341615A1 (de) | 2003-09-10 | 2005-04-28 | Basf Ag | Verfahren zur Herstellung von Xylylendiamin |
DE10341614A1 (de) | 2003-09-10 | 2005-04-28 | Basf Ag | Verfahren zur Herstellung von Xylylendiamin (XDA) |
DE10341613A1 (de) | 2003-09-10 | 2005-04-14 | Basf Ag | Verfahren zur Herstellung von Xylylendiamin |
DE10341632A1 (de) | 2003-09-10 | 2005-04-28 | Basf Ag | Verfahren zur Herstellung von Xylylendiamin |
DE10341633A1 (de) | 2003-09-10 | 2005-04-28 | Basf Ag | Verfahren zur Herstellung von Xylylendiamin |
DE10341612A1 (de) * | 2003-09-10 | 2005-04-28 | Basf Ag | Verfahren zur Herstellung von Xylylendiamin |
-
2003
- 2003-09-10 DE DE10341613A patent/DE10341613A1/de not_active Withdrawn
-
2004
- 2004-08-27 DE DE502004003420T patent/DE502004003420D1/de not_active Expired - Lifetime
- 2004-08-27 US US10/571,584 patent/US7541497B2/en not_active Expired - Fee Related
- 2004-08-27 EP EP04764542A patent/EP1663942B1/de not_active Expired - Lifetime
- 2004-08-27 WO PCT/EP2004/009568 patent/WO2005028417A1/de active IP Right Grant
- 2004-08-27 CN CNB2004800261326A patent/CN100361960C/zh not_active Expired - Fee Related
- 2004-08-27 JP JP2006525686A patent/JP4488527B2/ja not_active Expired - Fee Related
- 2004-08-27 AT AT04764542T patent/ATE358665T1/de not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2970170A (en) * | 1957-03-22 | 1961-01-31 | California Research Corp | Preparation of xylylenediamines |
GB1164354A (en) * | 1966-07-04 | 1969-09-17 | Toyo Rayon Co Ltd | Process for the Hydrogenation of Nitriles. |
EP1193244A2 (de) * | 2000-09-25 | 2002-04-03 | Mitsubishi Gas Chemical Company, Inc. | Verfahren zur Herstellung von Xylylendiamin |
EP1209146A1 (de) * | 2000-11-16 | 2002-05-29 | Basf Aktiengesellschaft | Verfahren zur Hydrierung von Nitrilen zu primären Aminen an Raney-Katalysatoren |
EP1279661A1 (de) * | 2001-07-16 | 2003-01-29 | Mitsubishi Gas Chemical Company, Inc. | Verfahren zur Herstellung von hochreinem Xylylendiamin |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7323598B2 (en) | 2003-09-10 | 2008-01-29 | Basf Aktiengesellschaft | Preparation of xylylenediamine (XDA) |
US7368610B2 (en) | 2003-09-10 | 2008-05-06 | Basf Aktiengesellschaft | Preparation of xylylenediamine (XDA) |
US7528284B2 (en) | 2003-09-10 | 2009-05-05 | Basf Aktiengesellschaft | Method for producing xylylenediamine (XDA) |
US7541497B2 (en) | 2003-09-10 | 2009-06-02 | Basf Aktiengesellschaft | Method for producing xylylenediamine (XDA) |
US7728174B2 (en) | 2005-08-02 | 2010-06-01 | Basf Se | Continuous hydrogenation processes for the preparation of xylylenediamines |
WO2007088131A3 (de) * | 2006-02-01 | 2007-10-04 | Basf Ag | Verfahren zur herstellung von reinem xylylendiamin (xda) |
CN101379021B (zh) * | 2006-02-01 | 2011-12-28 | 巴斯夫欧洲公司 | 纯苯二甲胺(xda)的制备方法 |
US8142618B2 (en) | 2006-02-01 | 2012-03-27 | Basf Aktiengesellschaft | Processes for preparing pure xylylenediamine |
Also Published As
Publication number | Publication date |
---|---|
DE502004003420D1 (de) | 2007-05-16 |
JP4488527B2 (ja) | 2010-06-23 |
ATE358665T1 (de) | 2007-04-15 |
US20070088179A1 (en) | 2007-04-19 |
DE10341613A1 (de) | 2005-04-14 |
CN100361960C (zh) | 2008-01-16 |
JP2007533614A (ja) | 2007-11-22 |
EP1663942A1 (de) | 2006-06-07 |
US7541497B2 (en) | 2009-06-02 |
CN1849295A (zh) | 2006-10-18 |
EP1663942B1 (de) | 2007-04-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1663943B1 (de) | Verfahren zur herstellung von meta-xylylendiamin (mxda) | |
EP1663942B1 (de) | Verfahren zur herstellung von meta-xylylendiamin (mxda) | |
EP1663945B1 (de) | Verfahren zur herstellung von xylylendiamin (xda) | |
EP1663944B1 (de) | Verfahren zur herstellung von xylylendiamin (xda) | |
EP1663946B1 (de) | Verfahren zur herstellung von xylylendiamin durch kontinuierliche hydrierung von flüssigem phthalodinitril | |
EP1663947B1 (de) | Verfahren zur herstellung von xylylendiamin durch kontinuierliche hydrierung von flüssigem phthalodinitril | |
EP1917232B1 (de) | Verfahren zur herstellung von xylylendiamin durch kontinuierliche hydrierung von phthalodinitril | |
DE102005036222A1 (de) | Verfahren zur Herstellung von Xylylendiamin durch kontinuierliche Hydrierung von flüssigem Phthalodinitril | |
WO2005026100A1 (de) | Verfahren zur herstellung von xylylendiamin (xda) | |
EP0105146B1 (de) | Verfahren zur Herstellung von Diaminen oder Diamingemischen | |
WO2005026101A1 (de) | Verfahren zur herstellung von xylylendiamin | |
WO2007033932A1 (de) | Verfahren zur herstellung von xylylendiamin | |
DE102004042947A1 (de) | Verfahren zur Herstellung von Xylylendiamin durch kontinuierliche Hydrierung von flüssigem Phthalodinitril | |
DE102004042954A1 (de) | Verfahren zur Herstellung von Xylylendiamin durch kontinuierliche Hydrierung von flüssigem Phthalodinitril | |
DE102005058417A1 (de) | Verfahren zur Herstellung von Xylylendiamin durch kontinuierliche Hydrierung von Phthalodinitril |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200480026132.6 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BW BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE EG ES FI GB GD GE GM HR HU ID IL IN IS JP KE KG KP KZ LC LK LR LS LT LU LV MA MD MK MN MW MX MZ NA NI NO NZ PG PH PL PT RO RU SC SD SE SG SK SY TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SZ TZ UG ZM ZW AM AZ BY KG MD RU TJ TM AT BE BG CH CY DE DK EE ES FI FR GB GR HU IE IT MC NL PL PT RO SE SI SK TR BF CF CG CI CM GA GN GQ GW ML MR SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2004764542 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007088179 Country of ref document: US Ref document number: 10571584 Country of ref document: US Ref document number: 2006525686 Country of ref document: JP |
|
DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWP | Wipo information: published in national office |
Ref document number: 2004764542 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 2004764542 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 10571584 Country of ref document: US |