+

WO2012034991A1 - Procédé de préparation de formamides - Google Patents

Procédé de préparation de formamides Download PDF

Info

Publication number
WO2012034991A1
WO2012034991A1 PCT/EP2011/065810 EP2011065810W WO2012034991A1 WO 2012034991 A1 WO2012034991 A1 WO 2012034991A1 EP 2011065810 W EP2011065810 W EP 2011065810W WO 2012034991 A1 WO2012034991 A1 WO 2012034991A1
Authority
WO
WIPO (PCT)
Prior art keywords
phase
formula
amine
formic acid
stream
Prior art date
Application number
PCT/EP2011/065810
Other languages
German (de)
English (en)
Inventor
Marek Pazicky
Thomas Schaub
Ansgar Gereon Altenhoff
Donata Maria Fries
Rocco Paciello
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2012034991A1 publication Critical patent/WO2012034991A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • C07C231/02Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines

Definitions

  • the present invention relates to a process for the preparation of formamides, i. of formamide and its / V-substituted derivatives starting from carbon dioxide.
  • Formamide and its derivatives are important selective solvents and extractants because of their polarity. They are z. B. for the extraction of butadiene from C 4 cuts, acetylene from C 2 cracker fractions and aromatics used from aliphatic.
  • Formamide, / V-Alkylformamide and A / ./V-dialkylformamide are prepared by reacting methyl formate with ammonia, / V-alkylamines or A /, / V-dialkylamines.
  • the liberated methanol can be recycled to the Methylformiatsynthese from carbon monoxide and methanol.
  • ammonia or the abovementioned amines are reacted at 20 to 100 ° C. and 2 to 10 MPa directly with carbon monoxide instead of methyl formate.
  • Work is carried out in methanol as a solvent with alkoxides as catalysts (Hans-Jürgen Arpe, Industrial Organic Chemistry, 6th edition, 2007, pages 48 to 49).
  • the TOF value (Turn Over Frequency) is a measure of the efficiency of the catalyst and indicates how many moles of product per mole of catalyst and hour are formed, cf. J.F. Hartwig: Organotransition Metal Chemistry, 1st Edition, 2010, University Science Books, Sausalito, California, p. 545).
  • Carbon dioxide can also be hydrogenated in the presence of dimethylamine and homogeneously dissolved platinum complex compounds of the formula ⁇ -Pt 2 (Ph 2 P-CH 2 -PPh 2 ) 3 ) to dimethylformamide.
  • platinum complex compounds of the formula ⁇ -Pt 2 (Ph 2 P-CH 2 -PPh 2 ) 3
  • TOF values 57.3 are achieved (Schreiner, S., et al., J. Chem. Soc., Chem. Commun., 1988, pages 602-603).
  • An enormous increase in TOF was achieved by the use of homogeneously dissolved ruthenium complex compounds containing trialkyl phosphine ligands.
  • the highest TOF value was achieved after 70 hours with 6,000 in the hydrogenation of carbon dioxide at 100 ° C, 13 MPa carbon dioxide and 8 MPa hydrogen in the presence of dimethylamine in the form of ammonium carbamate.
  • the catalyst used was RuCl 2 [P (CH 3 ) 3 ] 4 (JACS, Table 7).
  • EP 0 095 321 A, EP 0 151 510 A and EP 0 181 078 A describe the hydrogenation of carbon dioxide in the presence of a homogeneous catalyst comprising a transition metal of subgroup VIII (group 8, 9, 10), a tertiary amine and a polar solvent to an adduct of formic acid and the tertiary amine known.
  • Ruthenium-based carbonyl, halide and / or triphenylphosphine-containing complex catalysts and rhodium-phosphine complexes are mentioned as preferred homogeneous catalysts.
  • the hydrogenation is carried out at a carbon dioxide partial pressure of up to 6 MPa, a hydrogen partial pressure of up to 25 MPa and a temperature of about room temperature to 200 ° C.
  • JP 1 1322687 shows that salts of formic acid and tertiary amines are obtained in the reaction of aliphatic aldehydes with formaldehyde in the presence of tertiary amines to give polyalcohols. These salts are previously unrecognizable by-products.
  • the application teaches the salts at 20 to 130 ° C with primary or secondary amines to formamides, tertiary amines and water to implement.
  • the water of reaction is preferably after addition of a solvent such as. B. toluene separated by azeotropic distillation.
  • FIG. 7 shows an integrated process concept for the synthesis and work-up of dimethylformamide:
  • the reaction effluent consists of two liquid phases, which are separated from each other.
  • the upper, toluene and catalyst-containing phase is concentrated and then returned to the synthesis stage.
  • the lower aqueous phase containing the target product dimethylformamide is back-extracted with toluene and worked up by distillation.
  • the target products formamide and its derivatives should be made accessible with high yields and selectivities.
  • the work-up of the reaction effluent from the reactor should be technically simple, require little energy, and be carried out exclusively with substances already present in the process, without additional auxiliaries.
  • the separation and recycling of the homogeneous hydrogenation catalysts in the synthesis step should be as efficient as possible.
  • This object is achieved by a process for the preparation of formamides of Formal la in the F and R 2 are independently hydrogen, linear or branched radicals having 1 to 15 carbon atoms, cycloaliphatic radicals having 5 to 10 carbon atoms, a substituted or unsubstituted phenyl radical and a
  • Phenyl, and R 1 and R 2 may be closed to a five- or six-membered ring which contains an oxygen atom, a ⁇ / - ⁇ - or N-R radical, where R 1 has the abovementioned meaning,
  • N-substituted and two or all three radicals can also be linked together to form a chain comprising at least four atoms, with the proviso that the total number of C atoms per molecule is at least 6,
  • the partial stream not recycled to the extraction unit III is returned to the tertiary amine-enriched liquid phase in the hydrogenation reactor I.
  • the catalyst to be used in the hydrogenation of carbon dioxide in the process according to the invention is preferably a homogeneous catalyst.
  • This contains an element from the 8th, 9th or 10th group of the periodic table, ie Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and / or Pt.
  • the catalyst contains Ru, Rh, Pd, Os, Ir and / or Pt, more preferably Ru, Rh and / or Pd, and most preferably Ru.
  • the elements mentioned above are homogeneously dissolved in the form of complex-like compounds in the reaction mixture.
  • the homogeneous catalyst is to be selected so that it is enriched together with the tertiary amine in the liquid phase (B). Under "enriched” is a distribution coefficient of the homogeneous catalyst
  • the liquid phase (A) is the phase containing the solvent enriched with the formic acid / amine adducts.
  • this also includes radicals such as -CH 2 -C 6 Hn.
  • Suitable radicals are, for example, be mentioned methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1- (2-methyl) propyl, 2- (2, "- 3nty
  • the unbranched or branched, acyclic or cyclic, aliphatic radical preferably contains at least 1 and preferably not more than 10 carbon atoms. In the case of an exclusively cyclic radical in the above-mentioned sense, the number of carbon atoms is 3 to 12 and preferably at least 4 and preferably at most 8 carbon atoms.
  • Preferred radicals are ethyl, 1-butyl, sec-butyl, 1-octyl and cyclohexyl.
  • the phosphine group can contain one, two or three of the above-mentioned unbranched or branched, acyclic or cyclic, aliphatic radicals. These can be the same or different.
  • the phosphine group contains three of the above-mentioned unbranched or branched, acyclic or cyclic, aliphatic radicals, with particular preference, all three radicals are the same.
  • Preferred phosphines are P (A7-C n H 2 n + i) 3 where n is 1 to 10, more preferably tri-n-butylphosphine, tri-n-octylphosphine and 1, 2-bis (dicyclohexylphosphino) ethane.
  • acyclic or cyclic, aliphatic radicals individual carbon atoms may also be substituted by> P-.
  • multidentate for example, bidentate or tridentate phosphine ligands are also included. These preferably contain the
  • the phosphine group contains radicals other than the abovementioned unbranched or branched, acyclic or cyclic, aliphatic radicals, these generally correspond to those which are customarily used in the case of phosphine ligands for organometallic complex catalysts. Examples include phenyl, tolyl and xylyl.
  • the organometallic complex compound may contain one or more, for example two, three or four, of the abovementioned phosphine groups having at least one unbranched or branched, acyclic or cyclic, aliphatic radical. The remaining ligands of the organometallic complex may be of different nature.
  • Examples which may be mentioned are hydride, fluoride, chloride, bromide, iodide, formate, acetate, propionate, carboxylate, acetylacetonate, carbonyl, DMSO, hydroxide, trialkylamine, alkoxide.
  • the homogeneous catalysts can be used both directly in their active form and starting from customary standard complexes such as [M (p-Cymene) Cl 2 ] 2, [M (benzene) Cl 2 ] n , [M (COD) (allyl)], [MCI 3 x H 2 O], [M (acetylacetonate) 3 ], [M (COD) Cl 2 ] 2 , [M ( DMSO) 4 CI 2 ] with M equal to element from the 8th, 9th or 10th group of the periodic table with the addition of the corresponding phosphine ligand or only under reaction conditions.
  • customary standard complexes such as [M (p-Cymene) Cl 2 ] 2, [M (benzene) Cl 2 ] n , [M (COD) (allyl)], [MCI 3 x H 2 O], [M (acetylacetonate) 3 ], [M (COD) Cl 2 ] 2 , [M ( DMSO)
  • Preferred homogeneous catalysts in the process according to the invention are [Ru (Pn-Bu 3 ) 4 (H) 2 ], [Ru (Pn-octyl 3 ) 4 (H) 2 ], [Ru (Pn-Bu 3 ) 2 (1, 2 bis (dicyclohexylphosphino) ethane) (H) 2 ], [Ru (Pn-Octyl 3 ) 2 (1, 2-bis (dicyclohexylphosphino) ethane) (H) 2 ], [Ru (PEt 3 ) 4 (H) 2 .
  • TOF values turn-over frequency
  • the amount of said metal component in the organometallic complex is generally from 0.1 to 5000 ppm by weight, preferably from 1 to 800 ppm by weight, and more preferably from 5 to 800 ppm by weight, based in each case on entire liquid reaction mixture in the hydrogenation reactor.
  • the distribution coefficient of the homogeneous catalyst based on the amount of ruthenium in the amine phase and the product phase containing the formic acid / amine adduct after hydrogenation in the range of P is greater than 0.5, more preferably greater than 1.0, and most preferably greater than 4.
  • the tertiary amine is selected and matched with the polar solvent such that the hydrogenation product forms two liquid phases and the tertiary amine in the upper phase is enriched in the hydrogenation reactor.
  • enriched is meant a weight fraction of> 50% of the free, that is not bound in the form of the formic acid / amine adduct, tertiary amine in the upper phase based on the total amount of free, tertiary amine in both liquid phases.
  • the proportion by weight is preferably> 90%.
  • the choice of tertiary amine is generally made by a simple experiment in which the solubility of the desired tertiary amine in both liquid phases is determined experimentally under the intended process conditions.
  • the upper phase may also contain parts of the polar solvent and a non-polar inert solvent.
  • the preferred tertiary amine to be used in the process according to the invention is an amine of the general formula (IVa)
  • NR 3 R 4 R 5 in which the radicals R 3 to R 5 are identical or different and independently of one another _ : - : __ 3n QC
  • Suitable amines of the formula (IVa) include: triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine , Tri-n-nonylamine, tri-n-decylamine, tri-n-undecylamine, tri-n-dodecylamine, tri-n-tridecylamine, tri-n-tetradecylamine, tri-n-pentadecylamine, tri-n hexadecylamine, tri- (2-ethylhexyl) amine. Dimethyldecylamine, dimethyldodecylamine, dimethyl-tetradecylamine, ethyl-di (2-propyl) amine, dioctylmethylamine, dihexylmethylamine.
  • Triphenylamine methyldiphenylamine, ethyldiphenylamine, propyldiphenylamine, butyldiphenylamine, 2-ethylhexyldiphenylamine, dimethylphenylamine, diethylphenylamine, dipropylphenylamine, dibutylphenylamine, bis (2-ethylhexyl) phenylamine, tribenzylamine, methyldibenzylamine, ethyldibenzylamine and theirs by a or a plurality of methyl, ethyl, 1-propy, 2-propyl, 1-butyl, 2-butyl or 2-methyl-2-propyl groups substituted derivatives.
  • DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
  • DABCO 1, 4-diazabicyclo [2.2.2] octane
  • tropane N-methyl-8-azabicyclo [3.2.1 ] octane
  • garnetane N-methyl-9-azabicyclo [3.3.1] nonane
  • 1-azabicyclo [2.2.2] octane quinuclidine
  • the tertiary amine is an amine of general formula (IVa), in which the radicals R 1 to R 3 are independently selected from the group d- to C 2 alkyl, C 5 - to C 8 - Cycloalkyl, benzyl and phenyl.
  • a saturated amine i. containing only single bonds of the general formula (IVa).
  • a tertiary amine is an amine of the general formula (IVa) in which the radicals R 3 to R 5 are independently selected from the group C 5 - to C 8 -alkyl, in particular tri-n - pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, dimethylcyclohexylamine, methyldicyclohexylamine, dioctylmethylamine and dimethyldecylamine.
  • the radicals R 3 to R 5 are independently selected from the group C 5 - to C 8 -alkyl, in particular tri-n - pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, dimethylcyclohexylamine, methyldicyclohexylamine, dioctylmethylamine and dimethyldecylamine.
  • the tertiary amine used is an amine of the general formula (IVa) in which the radicals R 1 to R 3 are selected independently of one another from C 5 - and C 6 -alkyl.
  • the tertiary amine is preferably liquid in all process stages. However, this is not a mandatory requirement. It would also be sufficient if the tertiary amine were at least dissolved in suitable solvents. Suitable solvents are in principle those which are chemically inert with regard to the hydrogenation of carbon dioxide and the thermal cleavage of the adduct, in which the tertiary amine and, in the case of the use of a homogeneous catalyst, these also dissolve well, inversely polar solvent and formic acid / Dissolve amine adducts poorly.
  • polar solvents such as aliphatic, aromatic or araliphatic hydrocarbons, such as octane and higher alkanes, toluene, xylenes.
  • the polar solvent to be used in the hydrogenation of carbon dioxide in the process according to the invention is to be selected or matched with the tertiary amine in such a way that the polar solvent is enriched in the lower phase.
  • enriched is meant a weight fraction of> 50% of the polar solvent in the lower phase based on the total amount of polar solvent in both liquid phases.
  • the proportion by weight of the polar solvent is generally given by a A simple experiment in which the solubility of the desired polar solvent in both liquid phases under the intended process conditions is determined experimentally.
  • the polar solvent may be a pure polar solvent as well as a mixture of various polar solvents as long as the solvent, above-mentioned conditions, boiling point and phase behavior apply.
  • Suitable classes of substances which are suitable as polar solvents are preferably alcohols and diols and also their formic esters and water.
  • Suitable alcohols include alcohols in which the trialkylammonium formates preferably dissolve in a mixture with water and this product phase has a mixture gap with the free trialkylamine.
  • suitable alcohols are methanol, ethanol, 2-methoxyethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol.
  • the ratio of alcohol to water should be selected such that, together with the trialkylammonium formate and the trialkylamine, a biphasic mixture is formed in which most of the trialkylammonium formate, water and polar solvent are in the lower phase, generally by a simple Experiment is determined by experimentally determining the solubility of the desired polar solvent mixture in both liquid phases under the intended process conditions.
  • Suitable classes of compounds which are suitable as polar solvents are preferably diols and also their formic acid esters, polyols and also their formic acid esters, sulfones, sulfoxides, open-chain or cyclic amides and mixtures of the mentioned classes of substances.
  • diols and polyols examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol and called glycerin.
  • sulfone especially tetramethylene sulfone (sulfolane) is called.
  • Suitable sulfoxides are dialkyl sulfoxides, preferably C 1 - to C 6 -dialkyl sulfoxides, in particular dimethylsulfoxide.
  • suitable open-chain or cyclic amides are formamide, N-methylformamide, A / ./V-dimethylformamide, / V-methylpyrrolidone, acetamide and / V-methylcaprolactam.
  • the molar ratio of the polar solvent or solvent mixture to be used in the process according to the invention to the tertiary amine used is generally 0.5 to 30 and preferably 1 to 20.
  • the carbon dioxide to be used in the hydrogenation of carbon dioxide can be solid, liquid or gaseous. It is also possible to use gas mixtures containing large quantities of carbon dioxide, provided they are substantially free of carbon monoxide (volume fraction of ⁇ 1% CO).
  • the hydrogen to be used in the hydrogenation of carbon dioxide is generally gaseous. Carbon dioxide and hydrogen may also contain inert gases, such as nitrogen or noble gases. Advantageously, however, their content is below 10 mol% based on the total amount of carbon dioxide and hydrogen in the hydrogenation reactor. While larger amounts may also be tolerable, they generally require the use of a higher pressure in the reactor, requiring further compression energy.
  • the hydrogenation of carbon dioxide takes place in the liquid phase preferably at a temperature of 20 to 200 ° C and a total pressure of 0.2 to 30 MPa abs.
  • the temperature is at least 30 ° C and more preferably at least 40 ° C and preferably at most 150 ° C, more preferably at most 120 ° C and most preferably at most 80 ° C.
  • the total pressure is preferably at least 1 MPa abs and more preferably at least 5 MPa abs and preferably at most 15 MPa abs.
  • the partial pressure of the carbon dioxide is generally at least 0.5 MPa and preferably at least 2 MPa and generally at most 8 MPa.
  • the partial pressure of hydrogen is generally at least 0.5 MPa and preferably at least 1 MPa and generally at most 25 MPa and preferably at most 10 MPa.
  • the molar ratio of hydrogen to carbon dioxide in the feed of the hydrogenation reactor is preferably 0, 1 to 10 and particularly preferably 1 to 3.
  • the molar ratio of carbon dioxide to tertiary amine in the feed of the hydrogenation reactor is generally 0, 1 to 10 and preferably 0.5 to 3.
  • all reactors which are fundamentally suitable for gas / liquid reactions under the given temperature and the given pressure can be used as hydrogenation reactors.
  • Suitable standard reactors for liquid-liquid reaction systems are described, for example, in KD Henkel, "Reactor Types and Their Industrial Applications", in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007.
  • b04_087 chapter 3.3 "Reactors for gas-liquid reactions”. Examples which may be mentioned stirred tank reactors, tubular reactors or bubble column reactors.
  • the hydrogenation of carbon dioxide can be carried out batchwise or continuously in the process according to the invention.
  • the reactor is equipped with the desired liquid and optionally solid feedstocks and auxiliaries, and then carbon dioxide and hydrogen are pressed to the desired pressure at the desired temperature.
  • the reactor is generally depressurized and the two liquid phases formed are separated from one another.
  • the feedstocks and auxiliaries, including carbon dioxide and hydrogen are added continuously. Accordingly, the liquid phase is continuously removed from the reactor, so that the liquid level in the reactor remains the same on average. Preference is given to the continuous hydrogenation of carbon dioxide.
  • the average residence time in the hydrogenation reactor is generally 10 minutes to 5 hours.
  • the formic acid / amine adducts formed in the hydrogenation of carbon dioxide in the presence of the catalyst to be used, the polar solvent and the tertiary amine generally have the general formula (IIa)
  • the respective average compositions of the amine-formic acid ratios in the product phases in the respective process steps, ie the factor x can be determined, for example, by determining the formic acid content by titration with an alcoholic KOH solution against phenolphthalein and the amine content by gas chromatography.
  • the composition of the formic acid / amine adducts, ie the factor x can change during the different process steps. For example, adducts are generally formed after removal of the polar solvent a higher formic acid content with x 2 > Xi with x 2 1 to 4, wherein the excess, free amine can form a second phase.
  • the lower phase is enriched with the formic acid / amine adducts as well as the polar solvent.
  • a distribution coefficient of the formic acid / amine adducts P [concentration of formic acid / amine adduct (II) in liquid phase (A)] / [concentration of formic acid / amine adduct (II) in Liquid phase (B)] of> 1, where A and B have the meaning given above.
  • the distribution coefficient is> 2 and more preferably> 5.
  • the upper phase is enriched with the tertiary amine. In the case of the use of a homogeneous catalyst this is also enriched in the upper phase.
  • the two liquid phases formed are separated from one another in the process according to the invention and the upper phase is recycled to the hydrogenation reactor.
  • a further liquid phase comprising both liquid phases containing unconverted carbon dioxide and a gas phase containing unconverted carbon dioxide and / or unreacted hydrogen to the hydrogenation reactor.
  • phase separation vessels are, for example, standard apparatuses and standard methods, which are described, for example, in E. Müller et al. , "Liquid Liquid Extraction", in Ullmann's Encyclopaedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007.b03_06, Chapter 3 "Apparatus".
  • the liquid phase enriched with the formic acid / amine adducts as well as the polar solvent is heavier and forms the lower phase.
  • the phase separation can be carried out, for example, after relaxation, for example to about or near atmospheric pressure, and cooling of the liquid reaction mixture, for example to about or near ambient temperature.
  • relaxation for example to about or near atmospheric pressure
  • cooling of the liquid reaction mixture for example to about or near ambient temperature.
  • at least part of the at the higher reaction pressure in the Liquid phases of dissolved gas, in particular carbon dioxide degassed in the relaxation and to compress separately as a gas stream and is recirculated to the hydrogenation reactor.
  • the lower phase before being returned to the hydrogenation reactor separately to bring to reaction pressure.
  • a suitable, designed according to the pressure difference to be overcome designed compressor or a pump, which also consumes additional energy during operation for the recirculating gas and liquid phase.
  • the solvent and the amine are preferably to be selected so that the separation of the one, enriched with the formic acid / amine adducts and the polar solvent lower phase of the other, enriched with the tertiary amine upper phase, and the return of the upper phase to Hydrogenating reactor can be carried out at a pressure of 1 to 30 MPa abs.
  • the pressure is preferably at most 15 MPa abs.
  • the process according to the invention can thus preferably be carried out in such a way that the pressure in the hydrogenation reactor and in the phase separation vessel is the same or approximately the same.
  • the process according to the invention can thus preferably be carried out in such a way that the pressure and the temperature in the hydrogenation reactor and in the phase separation vessel are the same or approximately the same, whereby a pressure difference of up to +/- 0.5 MPa or approximately a temperature difference of up to +/- 5 ° C is understood.
  • the phase separation takes place at a pressure of at least 50%, very particularly preferably of at least 90% and in particular of at least "-gpression pressure.
  • the pressure during the phase separation is particularly high preferably at most 105% and most preferably at most 100% of the reaction pressure.
  • both liquid phases can separate very well even at an elevated temperature which corresponds to the reaction temperature.
  • the phase separation also no cooling and subsequent heating of the recirculating upper phase is required, which also saves energy.
  • the findings for the phase separation under elevated pressure and elevated temperature are exceeded even more that just the upper phase according to the inventive system under pressure by suitable choice of the amine and the polar solvent can have a particularly high absorption capacity for carbon dioxide. This means that any excess carbon dioxide which is not reacted in the hydrogenation reaction is very preferably present in the upper phase and can thus be recycled without problems as a liquid to the reactor.
  • the majority of the polar solvent of the separated lower phase is thermally separated from the formic acid / amine adducts in a distillation unit, whereby the polar solvent removed by distillation is recycled to the hydrogenation reactor.
  • the pure formic acid / amine adducts and free amine are obtained in the bottom of the distillation unit, since formic acid / amine adducts with a lower amine content are formed during the removal of the polar solvent, resulting in a two-phase bottom mixture consisting of an amine and a formic acid / amine Adduct phase forms ( Figure 2).
  • the thermal separation of the polar solvent or mixture is preferably carried out at a bottom temperature at which no free formic acid forms from the formic acid / amine adduct having the higher (x1) or lower (x2) amine content at a given pressure
  • the bottom temperature of the thermal separation unit is at least 20 ° C, preferably at least 50 ° C and more preferably at least 70 ° C, and generally at most 210 ° C, more preferably at most 190 ° C.
  • the pressure is generally at least 0.0001 MPa abs, preferably at least 0.005 MPa abs and more preferably at least 0.01 MPa abs and generally at most 1 MPa abs and preferably 0, 1 MPa abs.
  • the thermal separation of the polar solvent or mixture takes place either in an evaporator or in a distillation unit, consisting of evaporator and column, filled with packing, packing and / or trays.
  • ien- r rennun g be condensed, again with the liberated condensation enthalpy can be used, for example, to preheat the solvent coming from the extraction with amine / formic acid adduct mixture to the evaporation temperature (FIG. 1). Alternatively, only parts of the solvent mixture can be separated. It is also possible to separate the polar solvent only in substep VI and to return it to the hydrogenation stage I.
  • the solution of tertiary amine adduct and formic acid is extracted with free tertiary amine streams from the appropriate phase separation vessels and recycled to the hydrogenation reactor. This is done to separate residual amounts of hydrogenation catalyst from the product stream. This extraction allows efficient recovery of the expensive, active noble metal catalyst for the hydrogenation reaction.
  • the extraction takes place at temperatures of 30 to 100 ° C and pressures of 0, 1 to 8 MPa.
  • the extraction can also be carried out under hydrogen pressure.
  • the extraction of the hydrogenation catalyst can be carried out in any suitable apparatus known to the person skilled in the art, preferably in countercurrent extraction columns, mixer-settler cascades or combinations of mixer-settlers.
  • a device for adsorbing traces of hydrogenation catalyst may be advantageous to integrate a device for adsorbing traces of hydrogenation catalyst between the extraction apparatus and the thermal separation device.
  • Many adsorbents are suitable for adsorption. Examples include polyacrylic acid and its salts, sulfonated polystyrenes and their salts, activated carbons, montmorillonites, bentonites, silica gels and zeolites. If the amount of hydrogenation catalyst in the product stream of the phase separation vessel II is less than 1 ppm, in particular less than 0.1 ppm, the adsorption device is sufficient for the separation of the hydrogenation catalyst and its recovery. Then, the extraction step can be omitted and the tertiary amine can be recycled together with the organic solvent in the hydrogenation.
  • the reaction is carried out in the presence of the polar solvent used in the hydrogenation reactor.
  • the entire amount of polar solvent arriving in the reactor is preferably used.
  • the reaction is preferably carried out at temperatures of 80 to 200 ° C, preferably 100 to 180 ° C, particularly preferably 120 to 170 ° C.
  • the pressure is 0.01 to 10 MPa, preferably 0.1 to 7 MPa, particularly preferably 0.2 to 5 MPa.
  • reaction effluents in addition to formamides of the formula Ia, predominantly as intermediate formates of the formula Va, i.
  • the molar ratio of formic acid in adduct IIa to ammonia or amine III is 1 to 5, preferably 1 to 2, particularly preferably 1 to 1.
  • the reaction can be carried out batchwise, but preferably continuously.
  • formamides 1a can be carried out in standard reactors, as described, for example, in KD Henkel, "Reactor Types and their Industrial Applications” in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag, Chapter 3.3 are indicated. Examples which may be mentioned stirred tank reactors, tubular reactors or bubble column reactors.
  • part or all of the polar solvent is removed by distillation before being fed to the formamide reactor and recycled to the hydrogenation reactor (I).
  • the amount of polar solvent removed can be from 25 to 99%, preferably from 35 to 97%, particularly preferably from 50 to 95%, of the amount of polar solvent present in the stream before being fed to the reactor.
  • This process variant is advantageous, for example, when used as the polar solvent in the hydrogenation of carbon dioxide primary alcohols such as methanol together with water. It is also possible in principle and may be advantageous to use a polar solvent other than the amidation step, in the reactor IV, in the hydrogenation step in the hydrogenation reactor I. For this purpose, the polar solvent is separated from the hydrogenation and recycled to the hydrogenation reactor I. In the amidation stage, a different polar solvent used in the hydrogenation step is used in reactor IV, which is separated again after amidation and in the reactor IV, in which the amidation is carried out, is recycled.
  • the carbon dioxide hydrogenation in the presence of methanol and water and the reaction of the adduct (IIa) can be carried out with ammonia in the presence of sulfolane.
  • Suitable polar solvents for the amidation are, for example, sulfones, sulfoxides or open-chain or cyclic amides.
  • the distillation can be carried out in the separation of low-boiling polar solvents such as the monohydric alcohols methanol, ethanol, propanols and butanols at atmospheric pressure or in vacuo.
  • low-boiling polar solvents such as the monohydric alcohols methanol, ethanol, propanols and butanols
  • diols working in a vacuum is preferred.
  • distillation units can be used as distillation units. At far apart boiling points of the adduct IIa and the polar solvent can, for. B. evaporators such as falling film evaporator can be used.
  • the distillation unit to be used generally comprises a distillation column containing packing, packing and / or trays.
  • the distribution coefficient is> 2, and more preferably> 5.
  • the liquid phase D is enriched with the tertiary amine resulting from the adduct II a.
  • the two liquid phases C and D formed are separated from one another in the process according to the invention.
  • the liquid phase D is returned to the extraction apparatus and serves there for the extraction of residual amounts of homogeneous, dissolved hydrogenation catalyst. If appropriate, it is desirable, for example, for discharging unwanted by-products or impurities, to remove some of the liquid phases C or D from the process.
  • the separation of the two liquid phases C and D is generally carried out by gravimetric phase separation. Suitable for this purpose are, for example, standard apparatus and standard methods, which are described, for example, in E. Müller et. Al., "Liquid-Liquid Extraction,” in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007. b03_06, Chapter 3 "Apparatus”.
  • the phase separation can be carried out, for example, after relaxation, for example to about or near atmospheric pressure, and cooling of the liquid reaction mixture, for example to about or near ambient temperature.
  • the liquid phase C is passed into a distillation unit VI and worked up there by distillation. It contains the target product formamide of the formula (Ia), optionally unreacted ammonia or amine of the formula (IIIa), water of reaction and polar solvents selected from the group of methanol, ethanol, propanols or butanols or from the group of diols.
  • the polar solvents are separated before being fed to the formamide reactor and recycled to the hydrogenation stage I.
  • the distillation unit VI consists of at least one, preferably two to three distillation columns. These columns contain, depending on the separation problems z. B. packing, packages and / or floors. If the polar solvents have not previously been separated off, the ethanol / water and propanol / water homoazeotrope in the case of ethanol and heteroazeotrope in the case of butanols are to be taken into account.
  • the water of reaction is discharged from the process.
  • Polar solvents are recycled to the hydrogenation stage, unreacted ammonia and unreacted amines III a to the reactor.
  • the target products, the formamides of the formula (Ia) are discharged from the process and, if necessary, fed to a preferably distillative fine purification.
  • adducts of the formula (IIa), formates of the formula (Va) or mixtures of adducts of the formula (IIa) and formates of the formula (Va) with amines of the formula (IIIa), preferably with ammonia and polar solvents Implemented distillation conditions.
  • the reaction takes place in a distillation apparatus, for example a distillation flask with attached distillation column.
  • Aliphatic, cycloaliphatic or aromatic hydrocarbons such as n-heptane, n-hexane, cyclohexane, methylcyclohexane, toluene, ethylbenzene, ortho, meta and para xylene and mixtures of these compounds can be used as nonpolar solvents. These compounds form heteroazeotrope with water.
  • the bottom temperatures of this distillation are 80 to 200 ° C, preferably 110 to 200 ° C, particularly preferably 135 to 190 ° C.
  • the pressure is 0.01 MPa to 10 MPa, preferably 0.1 MPa to 7 MPa, more preferably 0.2 to 5 MPa.
  • the water of reaction is distilled off together with the polar solvent.
  • the process according to the invention has particular advantages when constructing a large-scale production plant with "economy of scale" for the preparation of adducts of the formula (IIa) from tertiary amines and formic acid, which is used for the production of formic acid and of formamides I a.
  • the total content of formic acid in the formic acid / amine adduct was determined by titration with 0.1 N KOH in methanol potentiometrically using a Mettler Toledo DL50 titrator ®. From this, the turn-over frequency (TOF) and the reaction rate were calculated. The composition of the two phases was determined by gas chromatography. The ruthenium content was determined by atomic absorption spectroscopy (AAS). The parameters and results of the individual experiments are given in Table 1.
  • Example B-1 Table 2 shows that in the phase separation of a Wasserstoffrieraustrags 26.2 g of a lower phase were obtained which contained 6.1 wt .-% formic acid in the form of the formic acid / amine adduct and 33 ppm ruthenium.
  • This lower phase was stirred at room temperature under inert conditions three times for 10 minutes each with 26.2 g of tri-n-hexylamine. The phases were separated.
  • the ruthenium content of the extracted lower phase as determined by AAS analysis was 21 ppm ruthenium.
  • Example B-1 shows that the amount of ruthenium in the lower phase can be reduced by about 36% by extraction with the same tertiary amine already used in C0 2 hydrogenation. Additional extraction steps or continuous countercurrent extraction could further reduce the ruthenium content.
  • Example C-1 shows the distillative separation of the polar solvents methanol and water from a hydrogenation. At 120 ° C and 0.02 MPa, a distillate was obtained on a rotary evaporator, which contained all the methanol, 0.3 wt .-% formic acid and almost all water.
  • the biphasic bottom effluent (upper phase + lower phase) can be used for the amide preparation in reactor IV (FIGS. 1 and 2).
  • Hastelloy C autoclave equipped with a magnetic stirrer bar was placed under inert conditions with the formic acid tertiary amine adduct IIa and, optionally, a nominal solvent and water (see Table 4, Examples D-1 through D-19). filled. Subsequently, the autoclave was sealed. At room temperature dimethylamine, n-butylamine, or ammonia were pressed. Subsequently, the reactor was heated with stirring (700 rpm). After the desired reaction time, the autoclave was cooled and the reaction mixture was depressurized.
  • a two-phase product mixture was obtained, the upper phase consisting of the tertiary amine and the lower phase consisting of the corresponding amide, water and optionally polar solvent and optionally ammonium formate. Both phases were separated and weighed using a separatory funnel. The composition of the two phases was determined by gas chromatography and proton NMR spectroscopy. The parameters and results of the individual experiments are shown in Tables 4 to 6.
  • Example D-1 Example D-2 Example D-3 Example D-4 Example D-5
  • Solvent 72 g 4- No LM 72 g 1, 4- No LM 73 g 1, 4- (LM) Butanediol Butanediol Butanediol
  • Example D-1 1 Example D-12 Example D- Example D-14 Example D-15
  • Experimental result E-1 shows that the reaction of adduct IIa with n-butylamine in the presence of 1,4-butanediol as the polar solvent gives n-butylformamide in quantitative yield.
  • Example F-1 Example F-2 Example F-3 Example F-4 Example F-5
  • Trihexylamine 57 g Trihexylamine 16 g Trihexylamine
  • Figure 2 is a block diagram of a further preferred method for the preparation of
  • carbon dioxide, stream 1, and hydrogen, stream 2 are fed into the hydrogenation reactor I. Therein they are reacted in the presence of a catalyst containing an element from the 8th, 9th or 10th group of the periodic table, a tertiary amine and a polar solvent to formic acid-amine adducts.
  • a supplementary stream of tertiary amine, (stream 4a) may be provided to the hydrogenation reactor I.
  • the two-phase discharge from the hydrogenation reactor I (stream 3) is passed into the phase separation vessel II.
  • the phase separation vessel II In the phase separation vessel II there is a lower phase which is enriched with formic acid-amine adducts and the polar solvent, and an upper phase 4, which contains predominantly the tertiary amine in which the homogeneous catalyst is enriched enriched, and from the Phase separation vessel II is recycled to the hydrogenation reactor I.
  • the lower phase 5 is fed to an extraction apparatus III, wherein catalyst residues are extracted with the tertiary amine from the phase separation vessel V (stream 12).
  • the tertiary amine with the catalyst residues (stream 6) from the extraction unit III is recycled to the hydrogenation reactor I, the product phase 7 from the extraction unit III is fed to the reactor IV, wherein the reaction with ammonia or amines, stream IIIa, takes place.
  • the biphasic liquid effluent, stream 9, from the reactor IV is separated in a phase separation vessel V into a formamide-enriched liquid phase, stream 10, and a second tertiary amine-enriched liquid phase, stream 12, stream 12 being preferably introduced into the extraction apparatus III is recycled.
  • the enriched with the target product formamide liquid phase, stream 10 is separated by distillation in a distillation unit VI to yield the formamide, stream la, discharge of water, H 2 0, and unreacted ammonia or amine, stream 1 1, in the reactor IV and polar solvent (stream 8) which is recycled to the hydrogenation reactor.
  • the preferred embodiment shown in Figure 2 differs from the embodiment in Figure 1 only insofar as the extraction unit III is followed by a separation unit 111-1, for separating polar solvent. In the separation unit 111-1, the polar solvent is separated off and recycled as stream 8a into the hydrogenation reactor I.
  • a different from the hydrogenation stage solvent can be supplied, which is separated again in the distillation unit VI and as stream 1 1 in the amidation, in the reactor IV, recycled.
  • the product stream 7a from the separation unit 111-1 is substantially free of polar solvent, and is passed into the reactor IV.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de préparation de formamides par transformation de dioxyde de carbone (1) avec de l'hydrogène (2) dans un réacteur d'hydrogénation I en présence : d'un catalyseur, contenant un élément du 8ème, 9ème ou 10ème groupe du système périodique, d'une amine tertiaire, contenant au moins 6 atomes de carbone par molécule, ainsi que d'un solvant polaire, en formant des produits d'addition d'acide formique/amine comme intermédiaires, qui sont transformés ensuite avec de l'ammoniac ou des amines dans un réacteur, avec obtention d'un produit de réaction liquide à deux phases, dont on sépare par distillation la phase liquide enrichie en formamides, avec obtention du formamide.
PCT/EP2011/065810 2010-09-17 2011-09-13 Procédé de préparation de formamides WO2012034991A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10177307.5 2010-09-17
EP10177307 2010-09-17

Publications (1)

Publication Number Publication Date
WO2012034991A1 true WO2012034991A1 (fr) 2012-03-22

Family

ID=44658735

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/065810 WO2012034991A1 (fr) 2010-09-17 2011-09-13 Procédé de préparation de formamides

Country Status (2)

Country Link
AR (1) AR083024A1 (fr)
WO (1) WO2012034991A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8703994B2 (en) 2011-07-27 2014-04-22 Basf Se Process for preparing formamides and formic esters
US8742171B2 (en) 2011-06-09 2014-06-03 Basf Se Process for preparing formic acid
US8946462B2 (en) 2011-11-10 2015-02-03 Basf Se Process for preparing formic acid by reaction of carbon dioxide with hydrogen
WO2015121357A1 (fr) * 2014-02-17 2015-08-20 Bayer Technology Services Gmbh Procédé d'hydrogénation du dioxyde de carbone en formamides
CN112608240A (zh) * 2021-01-26 2021-04-06 张善荣 用四聚丙烯和氢氰酸合成n,n-二甲基癸胺的方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3530182A (en) 1967-12-26 1970-09-22 Shell Oil Co Formamide production
EP0095321A2 (fr) 1982-05-22 1983-11-30 BP Chemicals Limited Production de sels de formiates
EP0151510A1 (fr) 1984-01-14 1985-08-14 BP Chemicals Limited Préparation de sels de l'acide formique
EP0181078A1 (fr) 1984-09-29 1986-05-14 BP Chemicals Limited Procédé de préparation de l'acide formique
EP0652202A1 (fr) 1993-11-04 1995-05-10 Research Development Corporation Of Japan Procédé de préparation de l'acide formique et de ses dérivés
JPH11322687A (ja) 1998-05-12 1999-11-24 Koei Chem Co Ltd ホルムアミド類の製造方法
WO2008116799A1 (fr) * 2007-03-23 2008-10-02 Basf Se Procédé de production d'acide formique
WO2010149507A2 (fr) * 2009-06-26 2010-12-29 Basf Se Procédé de préparation d'acide formique

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3530182A (en) 1967-12-26 1970-09-22 Shell Oil Co Formamide production
EP0095321A2 (fr) 1982-05-22 1983-11-30 BP Chemicals Limited Production de sels de formiates
EP0151510A1 (fr) 1984-01-14 1985-08-14 BP Chemicals Limited Préparation de sels de l'acide formique
EP0181078A1 (fr) 1984-09-29 1986-05-14 BP Chemicals Limited Procédé de préparation de l'acide formique
EP0652202A1 (fr) 1993-11-04 1995-05-10 Research Development Corporation Of Japan Procédé de préparation de l'acide formique et de ses dérivés
JPH11322687A (ja) 1998-05-12 1999-11-24 Koei Chem Co Ltd ホルムアミド類の製造方法
WO2008116799A1 (fr) * 2007-03-23 2008-10-02 Basf Se Procédé de production d'acide formique
WO2010149507A2 (fr) * 2009-06-26 2010-12-29 Basf Se Procédé de préparation d'acide formique

Non-Patent Citations (15)

* Cited by examiner, † Cited by third party
Title
"Applied Homogeneous Catalysis with Organometallic Compounds", vol. 2, 1996, VCH VERLAGSGESELLSCHAFT, pages: 1058 - 1072
0. KRÖCHER, R. A. KÖPPEL, A. BAIKER, CHEM. COMM., 1997
0. KRÖCHER, R. A. KÖPPEL, A. BAIKER, CHEM. COMMUN., 1996, pages 1497
CHEMIE INGENIEUR TECHNIK, vol. 75, 2003, pages 877 - 883
DATABASE WPI Week 200011, Derwent World Patents Index; AN 2000-119385, XP002667658 *
E. MÜLLER ET AL.: "Ullmann's Encyclopedia of Industrial Chemistry", 2005, WILEY-VCH VERLAG GMBH & CO. KGAA, article "Liquid-Liquid Extraction"
E. MÜLLER: "Ullmann's Encyclopedia of Industrial Chemistry", 2005, WILEY-VCH VERLAG GMBH, article "Liquid-Liquid Extraction"
HANS-JÜRGEN ARPE: "Industrielle Organische Chemie", 2007, pages: 48 - 49
J.F. HARTWIG: "Organotransition Metal Chemistry", UNIVERSITY SCIENCE BOOKS, pages: 545
K. D. HENKEL: "Ullmanns Encyclopedia of Industrial Chemistry", 2005, WILEY-VCH VERLAG, article "Reactor Types and their Industrial Applications"
K.D. HENKEL: "Ullmann's Encyclopedia of Industrial Chemistry", WILEY-VCH VERLAG GMBH & CO. KGAA, article "Reactor Types and Their Industrial Applications"
P.G. JESSOP, Y. HSIAO, T. IKARIYA, R. NOYORI, JACS, vol. 118, 1996, pages 351 - 352
S. SCHREINER ET AL., J. CHEM. SOC., 1988, pages 602 - 603
TETRAHEDRON LETTERS, no. 5, 1970, pages 365 - 368
W. LEITNER, ANGEW. CHEM. INT. ED. ENGL., vol. 34, 1995, pages 2207 - 2221

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8742171B2 (en) 2011-06-09 2014-06-03 Basf Se Process for preparing formic acid
US8703994B2 (en) 2011-07-27 2014-04-22 Basf Se Process for preparing formamides and formic esters
US8946462B2 (en) 2011-11-10 2015-02-03 Basf Se Process for preparing formic acid by reaction of carbon dioxide with hydrogen
WO2015121357A1 (fr) * 2014-02-17 2015-08-20 Bayer Technology Services Gmbh Procédé d'hydrogénation du dioxyde de carbone en formamides
CN112608240A (zh) * 2021-01-26 2021-04-06 张善荣 用四聚丙烯和氢氰酸合成n,n-二甲基癸胺的方法

Also Published As

Publication number Publication date
AR083024A1 (es) 2013-01-23

Similar Documents

Publication Publication Date Title
EP2655310B1 (fr) Procédé de production d'acide formique par mise en réaction de dioxyde de carbone avec de l'hydrogène
EP2445860B1 (fr) Procédé de préparation d'acide formique
EP2588438B1 (fr) Procédé de production d'acide formique par mise en réaction de dioxyde de carbone avec de l'hydrogène
EP2588439B1 (fr) Procédé de production d'acide formique par mise en réaction de dioxyde de carbone avec de l'hydrogène
DE3205464C2 (de) Verfahren zur Herstellung von n-Octanol
EP2542516A2 (fr) Préparation de sels d'acides carboxyliques éthyléniquement insaturés par carboxylation d'alcènes
EP2588440A1 (fr) Procédé de production d'acide formique
WO2012034991A1 (fr) Procédé de préparation de formamides
EP2736872A1 (fr) Procédé permettant de fabriquer des foramides et des esters d'acide formique
EP2838872B1 (fr) Procédé de fabrication d'alcools ramifiés
WO2013004577A1 (fr) Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène
WO2013050367A2 (fr) Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène
WO2013068389A1 (fr) Procédé de préparation d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène
EP2602247B1 (fr) Procédé de nettoyage de pyrrolidones N-alkyl-substitués par hydrogénisation
DE102012112060A1 (de) Verfahren zur Herstellung von Formiaten
EP3010880B1 (fr) Procédé de préparation de 2-chlorodialkylbenzylamines par hydrogénation
DE69616913T2 (de) Verfahren zur Herstellung von 3,7-Dimethyl-5,7-octadien-1-ol oder Rosenoxid
EP2794540A1 (fr) Procédé de production d'acide formique
EP2794539B1 (fr) Procédé de préparation d'acide formique
DE102012016959A1 (de) Verfahren zur Herstellung von Ameisensäure durch Umsetzung von Kohlendioxid mit Wasserstoff
DE3246978A1 (de) Verfahren zur herstellung von aminen
DE102012014159A1 (de) Verfahren zur Herstellung von Methylformiat
EP2855409B1 (fr) Procédé de préparation de mélanges
DE102012112404A1 (de) Verfahren zur kombinierten Herstellung von Ameisensäure, Methylformiat, Formamidverbindungen und Metallformiaten
DE69002971T2 (de) Verfahren zur Rückgewinnung eines Katalysators zur Verwendung bei der Herstellung von 1-(4-isobutylphenyl)propionsäure.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11758437

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11758437

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务,不要输入任何密码和下载