CN101084183A - Method for continuously producing methylamines - Google Patents
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- CN101084183A CN101084183A CNA2005800440119A CN200580044011A CN101084183A CN 101084183 A CN101084183 A CN 101084183A CN A2005800440119 A CNA2005800440119 A CN A2005800440119A CN 200580044011 A CN200580044011 A CN 200580044011A CN 101084183 A CN101084183 A CN 101084183A
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 150000003956 methylamines Chemical class 0.000 title abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 122
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 64
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 26
- 239000010457 zeolite Substances 0.000 claims description 22
- 229910021536 Zeolite Inorganic materials 0.000 claims description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000002444 silanisation Methods 0.000 claims description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 238000005913 hydroamination reaction Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 48
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000004939 coking Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052680 mordenite Inorganic materials 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 208000012839 conversion disease Diseases 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000005870 Ziram Substances 0.000 description 3
- 229960004217 benzyl alcohol Drugs 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- -1 MMA Chemical compound 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- BIHPYCDDPGNWQO-UHFFFAOYSA-N 5-iai Chemical compound C1=C(I)C=C2CC(N)CC2=C1 BIHPYCDDPGNWQO-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004381 Choline salt Substances 0.000 description 1
- PGJBQBDNXAZHBP-UHFFFAOYSA-N Dimefox Chemical compound CN(C)P(F)(=O)N(C)C PGJBQBDNXAZHBP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002169 Metam Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 1
- 229960005286 carbaryl Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 235000019417 choline salt Nutrition 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AFCCDDWKHLHPDF-UHFFFAOYSA-M metam-sodium Chemical compound [Na+].CNC([S-])=S AFCCDDWKHLHPDF-UHFFFAOYSA-M 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229940031815 mycocide Drugs 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 229960000278 theophylline Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization 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
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for continuously producing methylamines by reacting methanol and/or dimethylether and/or trimethylamine with ammonia and/or monomethylamine in a reactor in the presence of an acidic, shape-selective molecular sieve as a catalyst. The invention is characterised in that the reaction is carried out in the presence of > 0vol % to 0.9 vol % hydrogen, in relation to the gaseous reactor inlet.
Description
The present invention relates to a kind of method for preparing methylamine (MA) in reactor by methyl alcohol and/or dme and/or Trimethylamine 99 and ammonia and/or single methylamine are reacted continuously.
Single methylamine (MMA) is for being used for the intermediate of synthetic drugs (for example theophylline), agricultural chemicals (first is prestige (carbaryl), metamsodium (metham sodium), carbofuran (carbofuran) how), tensio-active agent, photographic developer, explosive and solvent such as N-N-methyl-2-2-pyrrolidone N-(NMP).
Dimethylamine (DMA) is similarly the synthetic intermediate.Example based on the product of dimethylamine is mycocide and vulcanization accelerator (two ziram) (ziram (ziram)), tetramethyl-sulfo-peroxide two carbonic acid diamide (TMTD), tetramethyl thiourea (MTMT), whipping agent 1, the 1-dimethylhydrazine, various medicines, monomer such as dimethylaminoethyl acrylate methyl base amino-ethyl ester, solvent (N, dinethylformamide, N,N-dimethylacetamide), catalyzer [for example 2,4, two [(dimethylamino) methyl] phenol (DMP30) of 6-], sterilant tetramethyldiamidophosphoric fluoride (dimefax), tensio-active agent and ion exchange resin.
Trimethylamine 99 (TMA) is used to prepare choline salt, cationic starch, sterilizing agent, flotation agent, sweeting agent and ion exchange resin.
The N/C mol ratio with 0.8-4.0 under 250-400 ℃ temperature is used to select the shape synthesis of methylamines with narrow hole zeolite catalyst such as mordenite, ZK-5, Rho, erionite, chabazite, ferrierite or clinoptilolite.In the reaction of methyl alcohol and ammonia, the product mixtures of acquisition mainly comprises single methylamine (MMA) and dimethylamine (DMA), only comprises a small amount of Trimethylamine 99 (TMA).
In the embodiment 1 of EP-A2-1 077 084 (Mitsubishi Gas Chem.Comp.Inc.), be 1.9 at the N/C ratio, reaction pressure is 20 crust, and temperature is 320 ℃, and the GHSV behind the 6h is 2500h
-1Down, be 99.2% available from the methanol conversion measured on the shape H-mordenite of selecting of Tosoh (HSZ-630), wherein the MMA/DMA/TMA weight ratio of product mixtures is 32/52/16 weight %.
Use select the shape mordenite catalyst to dimethylamine Study on Selectivity (PEP-Review No89-3-4, SRI International, W.S.Fong, 1991) in, the amount of having found ammonia can change in wide region and not change selectivity.Wish N/C than low, because then less ammonia must be isolated and recirculation by distillation from reaction product.Yet should avoid using low-down N/C ratio because especially at N/C than being lower than under 1.0 the situation, form the by product that makes catalyst deactivation (coking).
Be used to prepare amine, be easy to by carbon laydown-coking inactivation in particular for the zeolite catalyst for preparing methylamine by ammonia and methyl alcohol.Volatility is little, and the higher carbon laydown of molecular weight especially can form through dehydrogenation on an acidic catalyst by making methyl alcohol.Impurities in raw materials such as aldehyde or hydrocarbon have quickened the coking of zeolite.
The coking of zeolite causes the reduction gradually of catalytic activity.Therefore methanol conversion reduces, and must take some countermeasures as reducing inlet amount or rising temperature of reaction.These two kinds of countermeasures have all increased industrial cost.
High reaction temperature has disadvantageous effect to methylamine synthetic selectivity.At high temperature, the ratio of undesirable Trimethylamine 99 (TMA) of formation increases.In addition, the low-boiling point material of formation such as methane may increase.In addition, coking is quickened under high reaction temperature.The carbon laydown that increases can cause catalyst pores seriously to be stopped up, thereby makes catalyzer must replace too early and externally regeneration.
Therefore the crucial purpose of catalyst development deposits or its formation of slowing down at least for avoiding coking in selecting shape amination catalysis field.
A possibility of instant materials flow (time-on-stream) of improving catalyzer is for making aldehyde and the hydrogenation of coking precursor that forms as intermediate by adding as the hydrogen of reductive agent and deposition being converted into volatile constituent.Inactivation is by slowing down with reductive agent hydrogen in-situ treatment.
Patent application EP-A-118 193 (ICI) has especially described the purposes of hydrogen in the regeneration zeolite catalyst.Make hydrogen or hydrogen and ammonia for this reason or pass through catalyzer by the hydrogen of inert gas dilution.Hydrogen content should be at least 5 volume %.In embodiment 6,5 zeolite methylamine catalysts are by regenerating at 18 crust and 365 ℃ of following hydrogen flushing 28h with 80 liters/h.Can increase to 95.1% by 89.7% by this method methanol conversion.
Also described at H
2Synthetic (claim 5) of the methylamine under existing.According to embodiment 7, the H in the charging
2Ratio is preferably 20-40 volume %.
The methylamine that patent application JP-A2-09 249 618 (Mitsui Toatsu Chem.Inc.) has described zeolite catalysis in the presence of hydrogen synthesizes.H in this teachings suggest charging
2Amount be that 1-50 mole % is (based on used NH
3Molar weight=volume % with methyl alcohol), 2-20 mole % especially.According to embodiment, use 9 volume % hydrogen.
Catalyst system therefor is the zeolite that handled with silicoorganic compound on its surface.Active centre inactivation (formation silicon dioxide layer) and/or zeolite pore inlet that this surface modification causes being positioned at outer surface of zeolite shrink.Other used catalyzer is for wherein carrying out the zeolite of ion-exchange with magnesium nitrate solution.
Owing to also add hydrogen except material benzenemethanol and ammonia, the feasible instant materials flow of carrying out the catalyzer of silanization or ion-exchange is significantly improved.Also claim and use to pollute that the methyl alcohol of 2000ppm formaldehyde is arranged at the most also is feasible and activity of such catalysts does not have big loss.Methanol dehydrogenation is that formaldehyde is the methylamine of the zeolite catalysis secondary reaction in synthetic.Described hydrogen program can make unconverted pollution have the methyl alcohol of aldehyde to be recirculated into to select shape synthetic in.In embodiment (in the table 1 the 3rd, be called " embodiment 1 "), methylamine synthesizes the WHSV at 0.72kg (MeOH)/kg (catalyzer)/h, carries out under the pressure of 290-296 ℃ temperature of reaction and 20 crust.Methyl alcohol and ammonia are with 1.6 N/C molar ratio reaction.Except methyl alcohol and ammonia, make the hydrogen of 9 volume % pass through catalyst bed.Because this method was claimed and can realize 92.2% methanol conversion after the reaction times of 3000h.The ratio of dimethylamine is 61.9 weight % (based on whole methylamines) in the reaction discharge.In not adding the Comparative Examples of hydrogen (in the table 1 first, " Comparative Examples 1 "), only realize 89.8% methanol conversion behind the 3000h, and the ratio of DMA is 59.3 weight %.In other embodiments, use the mordenite catalyst of silanization with different sodium contents.There is the methyl alcohol of 400-670ppm formaldehyde to study to using to pollute equally.In all cases, the hydrogen program has positive-effect to catalyst activity and selectivity after long reaction working time.
In patent application JP-A2-09 249 619 (Mitsui Toatsu Chem.Inc.), the zeolite that will stand metal ion exchanged is used for synthesis of methylamines in the presence of hydrogen.Described metal is all redox active metals.Especially select the metal of the 8-11 group of the periodic table of elements.The method condition of embodiment and Comparative Examples correspond essentially to above-mentioned patent application JP-A2-09 249 618 those conditions and with the H that is instructed
2Measure identical.
The object of the invention provides preparation methylamine (MMA, DMA, TMA; Especially improved economic means DMA).Present method is intended to overcome one or more shortcomings of art methods.Present method at first is intended to as far as possible optionally generate DMA, and next obtains the instant materials flow of high catalyzer.Catalyzer should slow down or avoid very significantly owing to pyrogenic inactivation.The industrial goods raw material that for example comprises aldehyde or toluene impurity or recycle stream be should allow to use and catalyst activity and instant materials flow can significantly do not reduced.
According to the present invention, recognize higher H in art methods
2Amount relates in particular to expensive at equipment and secure context.
Under the hydrogen content of the 1-20 volume % order of magnitude, in reactor, relate to extra significant cost, because must will be from NH with the hydrogen zeolite catalyst of for example regenerating continuously
3Recycle gas (the NH of the condenser of tower
3, H
2If, the mixture of TMA and suitable MMA and DM A) via compressor be recirculated into synthetic in.If cool off NH with river
3The condenser of tower, then recycle gas comprises about 80-90%NH usually
3And methylamine.
Ammonia (comprising TMA, MMA, DMA) must reclaim from purge stream via adsorption/desorption units, and this must increase not condensable gases (for example CO, CO
2, N
2, CH
4) concentration, and must not contain NH with what clean
3Hydrogen (having residual not condensable gases) burning.
Since uncondensed gas (recycle gas) ratio height, NH
3If the size of the condenser of tower must be than under the distillment total condensation distillment situation suitable with the reflux amount big (lower heat transfer coefficient, preferably lower condensing temperature).
On the other hand, if can be in reactor use-case according to appointment 0.1 volume % or hydrogen still less for example carry out the cyclic regeneration of zeolite catalyst, then will be from NH
3It is not absolute necessary that the uncooled part of the condenser of tower is recirculated in synthetic because even under the situation of perfect combustion the hydrogen ratio also lower, for example the MA throughput at device is the only about 50m of hydrogen ratio under the 100000t/a situation
3(S.T.P.)/h.Xiang Guan variable cost is compared low with other running cost therewith.
For reclaiming ammonia cut (comprising TMA, MMA, DMA), in existing amine exit gas separation (adsorption/desorption), exist enough free volumes to be used for the amount that produce this moment.
Therefore, find a kind of method for preparing methylamine in reactor by methyl alcohol and/or dme and/or Trimethylamine 99 and ammonia and/or single methylamine are reacted continuously, wherein said being reflected at based on the gas reactor charging carried out under existing for＞0 volume % to 0.9 volume % hydrogen.
Based on whole gases used NH
3With the molar weight of methyl alcohol, H in the reactor feed
2Described molar weight corresponding to described H
2Volume % amount.
Reaction is 0.001-0.8 volume %, especially 0.01-0.7 volume % based on the gas reactor charging in each case preferably, and very preferably 0.05-0.6 volume % for example carries out under the existence of the hydrogen of 0.1-0.5 volume % or 0.2-0.4 volume %.
Acidity, shape-selective molecular sieve as catalyzer are preferably zeolite, especially preferably have the zeolite of MOR, LTA, CHA, ERI, OFF, HEU, RHO, LEV, KFI, PHI, FAU, MFI structure type or its mix-configuration.
The zeolite that very particularly preferably will have MOR or CHA, RHO, a KFI structure type as acid, shape-selective catalyst (people such as D.R.Corbin, Catalysis Today 37,1997,71-102).
Under the situation of catalyst system therefor, preferably do not carry out the modification of surface and pore structure in advance.
For example at EP-A-593 086, JP 254256/1986, US 4,683,334, JP 262540/1991; J.Catal.1991,131,482; US 5,137, and 854, Shokubai, 1987,29,322, J.Chem.Soc., Chem.Commun.1982,819, WO 2004/002937 and J.Weitkamp, L.Puppe, Catalysis and Zeolites, the 1st edition, described in specialized textbook the 3rd chapter of Springer Verlag 1999, especially under the situation of catalyst system therefor, not in advance with P contained compound or with silanization compound treat surface in liquid phase, solid phase or gas phase in each case.
Under the situation of catalyst system therefor, preferably do not carry out ion-exchange in advance with basic metal and/or alkaline-earth metal ions.
The catalyzer air speed of showing with the methyl alcohol kilogram numerical table of every kg catalyst per hour is preferably 0.1-1.5h
-1, 0.2-1.2h especially
-1, 0.4-0.8h very especially
-1
N/C mol ratio based on raw material (all) is preferably 0.8-4.0, especially 1.4-2.5, very especially 1.7-2.2.
Reaction especially 280-320 ℃, is very especially carried out under 290-315 ℃ the temperature preferably at 250-400 ℃.
The absolute pressure of reaction is preferably the 10-50 crust, especially 15-30 crust, particularly 18-25 crust.
For the inventive method, methylamine is preferably with single methylamine (MMA): dimethylamine (DMA): Trimethylamine 99 (TMA)=＜40:＞50 :≤10, and MMA: DMA: TMA=≤36 especially: 〉=55 :≤9 weight ratio obtains.
In the particularly advantageous embodiment of the inventive method, with the NH that contains methylamine of this method
3/ H
2Waste streams (from the discharge gas of the condenser of ammonia tower) is used for hydroamination reaction, is particularly useful for by alcohol, aldehyde and/or the amination of ketone hydrogen are prepared amine.
Reaction is particularly preferably in carrying out under the isothermal condition, promptly deviation be no more than the regulation temperature of reaction+/-20 ℃, preferred+/-15 ℃, preferred especially+/-10 ℃, especially+/-5 ℃, very especially+/-4 ℃.
The reactor that is appropriate to this for example is at DE-A-34 14 717 (Linde AG, ' Lindereactor '), bundled tube reactor that is used for synthesis of methylamines or the isothermal reactor described in EP-A1-534 195 (BASF AG) and the WO-A1-04/048313 (BASF AG), or have intercooled adiabatic reactor.
In the specific embodiments of the inventive method, used methyl alcohol comprises 1-1000ppm, and especially the formaldehyde of 10-200ppm and/or used methyl alcohol and/or used ammonia respectively comprise 1-1000ppm, especially the toluene of 5-200ppm.
For example according to DD-125 533 (VEB Leuna-Werke), the aftertreatment of reactor discharge can be carried out based on those skilled in the art's currently known methods.
In specific embodiments of the present invention, optional Trimethylamine 99 (TMA) that uses and/or the optional single methylamine (MMA) that uses are each recycle stream from the aftertreatment of present method reaction product.
All ppm data in this article are all based on weight.
Embodiment
In laboratory experiment, the zeolite catalyst of the mordenite type of the not surface modification of the synthetic use of methylamine H form carries out.Experiment is carried out in diameter is the 100ml tubular reactor of 14mm.Reactor is operated (with three heating circuit electrically heated) under isothermal.Synthetic carry out and do not make reactive component recirculation with one way (straight pass).
Catalyzer is made up of the extrudate that changes fragment by the 1.6mm sieve into; The 0.5-1.6mm fraction is used for catalysis.In each case the 70ml catalyzer is used for experiment and fills remaining reactor volume with inert bed.Experiment is carried out under the absolute pressures of 290-350 ℃ temperature of reaction and 20 crust.The catalyzer air speed is 0.4-0.6kg (MeOH)/liter (catalyzer)/h.The N/C mol ratio is 1.8: 1.
The reaction discharge is by online gc analysis.Being separated in to optimize on the GC post (Varian CP-Volamine) be used for short chain amine of methylamine carried out, and thermal conductivity detector (TCD) is used for detecting.Measure the content of unconverted methyl alcohol and the activity of such catalysts of deriving thus.
Comparative Examples 1
In tubular reactor, methylamine synthesizes the catalyzer air speed at 0.6kg (MeOH)/liter (catalyzer)/h, carries out under the pressure of 310-350 ℃ temperature of reaction and 20 crust.
Reaction begins under 310 ℃ with live catalyst, in case and methanol conversion reduce to less than 93% just with 5 ℃ of temperature risings.Behind the total run time of 1150h, reached 350 ℃ maximum temperature of reaction; Further behind the reaction 50h, methanol conversion is reduced to very soon less than 80%.The catalyzer that shifts out has the carbon content of 4.2-6.5 weight %.
Comparative Examples 2
In the tubular reactor identical, under identical reaction conditions-temperature, mol ratio, air speed, use identical catalyzer with Comparative Examples 1.At 480h after the reaction times, except methyl alcohol and ammonia, (110 liters (S.T.P.)/liter (catalyzer)/h) (rising the volume under the temperature and pressure condition of (S.T.P.)=be converted to standard) passes through catalyst bed to make the hydrogen of 9.5 volume %.Catalyst deactivation significantly slows down.The temperature of reaction that only requires 350 ℃ after the working time of 2000h is to guarantee to surpass 93% methanol conversion.In a word, in the instant materials flow that before transformation efficiency is reduced to less than 80%, obtains 2070h under 350 ℃ the maximum temperature.The catalyzer that shifts out has the carbon content of 2.9-4.6 weight %.
Comparative Examples 3
In the tubular reactor identical with Comparative Examples 1, (the catalyzer air speed of MeOH/ liter (catalyzer)/h), the pressure of 290-350 ℃ temperature of reaction and 20 crust use identical catalyzer down at 0.4kg.In synthetic, directly using the N/C mol ratio is 1.8 methyl alcohol and ammonia.Reaction begins under 290 ℃ with live catalyst, in case and methanol conversion reduce to less than 90% just with 5 ℃ of temperature risings.Behind the total run time of 2550h, reached 350 ℃ maximum temperature; Further behind the reaction 80h, methanol conversion is reduced to very soon less than 80%.The carbon content of the catalyzer that shifts out is 3.0-7.4 weight %.
Embodiment 1
In the tubular reactor identical, under identical reaction conditions-temperature, mol ratio, air speed, use identical catalyzer with Comparative Examples 2.Except methyl alcohol and ammonia, make hydrogen pass through catalyst bed.In 1500h originally, be metered into 5 volume % hydrogen (40 liters (S.T.P.)/liter (catalyzer)/h).In the working time of 1500-6000h, be metered into 2.5 volume % hydrogen, and after 6000h, add 0.9 volume % hydrogen.After the operating time of 3600h, only reach 295 ℃ temperature.In this program, therefore only be issued to this working time at temperature microlitre height.In a word, the instant materials flow that surpasses 7000h obtains under 300 ℃ temperature of reaction, and should expect the total run time that significantly surpasses 8000h.
Comparative Examples 4
In tubular reactor, use 500h with synthesis of methylamines the clavate mordenite of 70mlH form air speed isothermal under 300 ℃ temperature of reaction with 0.4kg (MeOH)/liter (catalyzer)/h.Be reflected under the ammonia-methyl alcohol mol ratio of 20 bar pressures and 1.8 and directly carry out.Raw materials used is the ammonia and the methyl alcohol of industrial quality.Reaction conversion ratio is reduced to 96% by 99% in reaction process.The catalyzer that shifts out has the carbon content of 1.1-1.3 weight %.
Embodiment 2
In the tubular reactor identical, under identical reaction conditions-temperature, mol ratio, air speed, use identical catalyzer with Comparative Examples 4.Except methyl alcohol and ammonia, (7 liters (S.T.P.)/liter (catalyzer)/h) passes through catalyst bed to make the hydrogen of 0.9 volume %.Reaction conversion ratio is reduced to 97% by 99% in reaction process.The catalyzer that shifts out has the carbon content of 0.71-0.73 weight % and the nitrogen content of 2.2-2.4 weight %.
Comparative Examples 5
In the tubular reactor identical, use 500h with synthesis of methylamines same catalyst air speed isothermal with 0.4kg (MeOH)/liter (catalyzer)/h under 300 ℃ temperature of reaction with Comparative Examples 4.Be reflected under the ammonia-methyl alcohol mol ratio of 20 bar pressures and 1.8 and directly carry out.0.225 weight % formaldehyde solution (concentration is 37%, corresponding to be 830ppm formaldehyde based on methyl alcohol) is added in the material benzenemethanol (corresponding to 0.3g/ liter/h formaldehyde).Reaction conversion ratio is reduced to 88% by 99% in reaction process.The catalyzer that shifts out has the carbon content of 2.7-3.9 weight %.
Embodiment 3
In the tubular reactor identical, under identical reaction conditions-temperature, mol ratio, air speed, use identical catalyzer with Comparative Examples 5.Once more pollution there is the methyl alcohol of 0.225 weight % formaldehyde solution (concentration is 37%, corresponding to be 830ppm formaldehyde) to be used for synthesis of methylamines based on methyl alcohol.In addition, (7 liters (S.T.P.)/liter (catalyzer)/h) passes through catalyst bed to make the hydrogen of 0.9 volume %.Reaction conversion ratio is reduced to 95% by 99% in reaction process.The catalyzer that shifts out has the carbon content of 2.6-3.1 weight % and the nitrogen content of 2.1-2.6 weight %.
Comparative Examples 6
In the tubular reactor identical, use 500h with synthesis of methylamines same catalyst air speed isothermal with 0.4kg (MeOH)/liter (catalyzer)/h under 300 ℃ temperature of reaction with Comparative Examples 4.Be reflected under the ammonia-methyl alcohol mol ratio of 20 bar pressures and 1.8 and directly carry out.1000ppm toluene is added in the material benzenemethanol.Reaction conversion ratio is reduced to 90% by 99% in reaction process.The catalyzer that shifts out has the carbon content of 1.2-1.4 weight % and the nitrogen content of 2.2-2.5 weight %.
Claims (20)
1. method for preparing methylamine in reactor by methyl alcohol and/or dme and/or Trimethylamine 99 and ammonia and/or single methylamine are reacted continuously, wherein said being reflected at based on the gas reactor charging carried out under existing for＞0 volume % to 0.9 volume % hydrogen.
2. according to the process of claim 1 wherein that described being reflected at based on the gas reactor charging is to carry out under 0.001-0.8 volume % hydrogen exists.
3. according to the process of claim 1 wherein that described being reflected at based on the gas reactor charging is to carry out under 0.01-0.7 volume % hydrogen exists.
4. according to each method in the aforementioned claim, wherein said acidity, shape-selective molecular sieve are zeolite.
5. according to the method for claim 4, wherein said catalyzer is the zeolite with MOR, LTA, CHA, ERI, OFF, HEU, RHO, LEV, KFI, PHI, FAU, MFI structure type or its mix-configuration.
6. according to each method in the aforementioned claim, wherein under the situation of catalyst system therefor, do not carry out the modification of surface and pore structure in advance.
7. according to the method for claim 6, wherein under the situation of catalyst system therefor, the treat surface in liquid phase, solid phase or gas phase with P contained compound or silanization compound in advance not.
8. according to each method in the aforementioned claim, wherein under the situation of catalyst system therefor, do not carry out ion-exchange in advance with basic metal and/or alkaline-earth metal ions.
9. according to each method in the aforementioned claim, wherein the N/C mol ratio based on raw material is 0.8-4.0.
10. according to each method in the aforementioned claim, carry out under the wherein said 250-400 of being reflected at ℃ the temperature.
11., carry out under the wherein said 280-320 of being reflected at ℃ the temperature according to each method among the claim 1-9.
12., carry out under the absolute pressure of the wherein said 10-50 of being reflected at crust according to each method in the aforementioned claim.
13. according to each method in the aforementioned claim, wherein the described catalyzer air speed of showing with the methyl alcohol kilogram numerical table of every kg catalyst per hour is 0.1-1.5h
-1
14. according to each method in the aforementioned claim, wherein with single methylamine (MMA): dimethylamine (DMA): Trimethylamine 99 (TMA)=＜40:＞50 :≤10 weight ratio prepares methylamine continuously.
15. according to each method in the aforementioned claim, wherein with the NH that contains methylamine of described method
3/ H
2Waste streams (from the discharge gas of the condenser of ammonia tower) is used for hydroamination reaction.
16. according to each method in the aforementioned claim, wherein said being reflected under the isothermal carried out.
17. according to each method in the aforementioned claim, wherein used methyl alcohol comprises 1-1000ppm formaldehyde.
18. according to each method in the aforementioned claim, wherein used methyl alcohol and/or used ammonia respectively comprise 1-1000ppm toluene.
19. according to each method in the aforementioned claim, wherein used Trimethylamine 99 is the recycle stream from the aftertreatment of described method reaction product.
20. according to each method in the aforementioned claim, wherein used single methylamine is the recycle stream from the aftertreatment of described method reaction product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004062718.5 | 2004-12-21 | ||
| DE200410062718 DE102004062718A1 (en) | 2004-12-21 | 2004-12-21 | Process for the continuous production of methylamines |
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| EP (1) | EP1831148A1 (en) |
| JP (1) | JP2008524286A (en) |
| CN (1) | CN101084183A (en) |
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| WO (1) | WO2006066838A1 (en) |
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| WO2007036478A1 (en) | 2005-09-29 | 2007-04-05 | Basf Se | Moulding containing an aluminosilicate and aluminium oxide and method of continuously producing methylamines |
| JP6441116B2 (en) * | 2015-02-18 | 2018-12-19 | 住友精化株式会社 | Methylamine purification apparatus and methylamine purification method |
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| JP2008524286A (en) | 2008-07-10 |
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