• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    A nonaqueous hydroformylation process for producing aldehydes using low volatile, organic soluble monosulfonated tertiary phosphine salt ligands.
    公开号:SU1715202A3
    申请号:SU874202974
    申请日:1987-07-10
    公开日:1992-02-23
    发明作者:Джордж Абатеглоу Энтони；Роберт Бринт Дэвид
    申请人:Юнион Карбид Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved method for the production of C4-C13-aldehydes by hydroformylation, catalyzed by the transition metal-phosphorus complex, using monosulphated salt of tertiary phosphine as ligands.
    The goal of iService is to simplify the process technology.
    Example. A series of different precursors of the rhodium complex catalyst is prepared in the form of a solution containing the practically solubilized rhodium dicarbonylacetylacetonate reaction product and various ligands, triphenylphosphine monosulfonic acid salts, and used to hydroformylate propylene to C4 aldehydes as follows.
    Rhodium dicarbonyl acetylacetonate is mixed at room temperature with various ligands — triphenylphosphine monosulfonates of the general formula
    : sox
    where M means a radical and a sufficient amount of Texanol (monoisobutyrate
    2,2,4-trimethyl-1,3-pentadiol) as a solvent to obtain solutions of various rhodium catalytic precursors containing the amounts of rhodium and ligand given in table. one,
    Each solution of the rhodium catalytic precursor prepared in this way is then used to hydroformylate propylene in a 100 ml stainless steel autoclave with magnetic stirring, and the autoclave is connected to the pipeline to introduce gases to the required partial pressure. The autoclave is also equipped with a pressure indicator to determine the reaction pressure up to 0.0007 kg / cm and a thermometer with platinum resistance to determine the temperature of the reaction solution to ± 0.10 ° C. The reactor is heated from the outside with two 200 W heaters themselves. The temperature of the reaction solution is monitored by a plate impedance sensor connected to an external proportional temperature controller to control the temperature of the external heating strips.
    For each non-aqueous hydroformylation reaction, about 15 ml (about 14 g) of the rhodium catalytic precursor solution previously prepared are loaded into the reaction autoclave in a stream of nitrogen and heated to the applied reaction temperature. Then the reactor is blown up to 0.352 kg / cm and a pre-mixed mixture of gases of 1: 1: 1 carbon monoxide, hydrogen and propylene is introduced into the reactor through a gas pipeline and hydroformylated propylene in this way.
    The rate of hydroformylation reaction (g-mol / k / h of C4-aldehydes) from a sequential step change in pressure of 0.352 kg / cm in the reactor is determined by measuring the nominal operating pressure in the reactor, while the molar ratio of linear (n-butyraldehyde) to branched (2-methylpropionaldehyde) product is measured by gas chromatography. The results are shown in Table. one.
    PRI mme R 2. Use the procedure of Example 1 to prepare a solution of a rhodium catalytic precursor using rhodium dicarbonylacetylacetonate, Texanol as the solvent, and various ligands, cyclohexyl diphylphosphine monosulfonates of the general formula
    soX
    where M is a quaternary trioctyl or dimethyldodecylammonium radical. Propylene hydroformylation is repeated using the solutions of the precursors of the rhodium complex catalysts and the hydroformylation reaction conditions given in Table. 2, Determine the rate of hydroforming reaction (in g-mol / l / h of the C4-aldehydes obtained), as well as the molar ratio of linear (n-butyraldehyde) to the branched product (2-methylpropionaldehyde). PRI me R 3. Use the procedure of Example 1 to prepare a solution of a rhodium catalytic precursor using rhodium dicarbonyl acetylacetonate, Texanol as the solvent, and various ligands, dicyclohexylphosphine monosulfonates of the general formula
    sdjM
    where M is a quaternary trioctyl or dimethyldodecylammonium radical. Propylene hydroformylation is repeated using the reaction conditions and the type of rhodium precursor solution.
    complex catalyst, are given in table. 3. Determine the rate of hydroformylation reaction (in g-mol / l / h of the obtained C4-aldehydes). as well as the molar ratio of linear (n-butyraldehyde)
    to a branched (2-methylpropionaldehyde) aldehyde product.
    Example 4: Using the procedure of Example 1, a solution of a rhodium catalytic precursor is prepared from rhodium dicarbonylacetylacetonate, Texanol as a solvent and a monosulfonated tertiary phosphine salt. Hydroformylate butene-1 using solutions of the rhodium complex precursor
    catalyst and the reaction conditions given in table. 4. The ligand — the monosulfonated tertiary phosphine salt used in Quest 1 is a cyclohexyldiphenylphosphine trioctylammonium sulfonate (CHDCHmS) of formula
    P-Q 0 80 (C8H „) h
    whereas the ligand used in Test 2 is the dicyclohexylphenylphosphine trioctylammonium sulfonate (DCGFMS) of formula
    SOj iHlCgHi,),
    The rate of hydroformylation reaction (in g-mol / l / h obtained by Cb-aldehydes) is determined, as well as the molar ratio of linear (n-valeraldehyde) to the branched (2-m-yl butyral hydride) aldehyde product.
    Example 5 Use the procedure of Example 1 to prepare a solution of a rhodium catalyst precursor using rhodium dicarbonylacetylacetonate, Texanol as the solvent, and the monosulfonated triphenylphosphine ligand of the formula
    (Cnhsl
    SO, NH (CH,).
    / jj-i a.i v / jLli / o
    and yuthydroformylation of dodecene-1 using solutions of various precursors of rhodium complex catalysts and various conditions of the hydroformylation reaction given in Table. 5. Determine the rate of hydroformylation reaction (in g-mol / l / h obtained C 1 3 -aldehydes), as well as the molar ratio of linear (tridecanal) to branched (2-methyldodecanal) aldehyde product.
    Example Continuous hydroformylation of butene-1 is carried out using a ligand, a monosulfonated triphenylphosphine salt, as follows.
    Non-aqueous hydroformylation is carried out in a glass reactor in the mode of continuous hydroformylation — with one pass of butene-1. The reactor is a pressure flask immersed in an oil bath with a glass viewing window. Approximately 20 ml of a freshly prepared solution of the rhodium catalyst precursor is loaded into the reactor with a syringe, then the system is flushed with nitrogen. The precursor solution contains about 300 ppm rhodium, administered as dicarbonylacetylacetone rhodium, about 15 May.% (About 80 molar equivalents of ligand per 1 mole of rhodium) of the ligand monosulfonated triphenylphosphine salt of the formula
    ,)
    and Texanol as a solvent. After closing the reactor, the system is purged with nitrogen again and the oil bath is heated to the required hydroformylation reaction temperature. The hydroformylation reaction is carried out at a total gas pressure of about 11.25 kg / cm, the partial pressures of hydrogen, carbon monoxide and butene-1 are given in Table. 6, the rest is
    nitrogen and aldehyde product.
    The feed gas streams (carbon monoxide, hydrogen, butene-1 and hydrogen) are individually controlled by mass flow meters and the feed gases are dispersed
    in the solution of the precursor with the help of sprinklers (bubblers) made of stainless steel. The unreacted portion of the feed gases is distilled off with a Cz-aldehyde product and the exhaust gas is analyzed for 14 days of continuous operation. The average daily reaction rate (in g-mol / l / h of the Sb-aldehyde product) and the molar ratio of the linear (n-valeraldehyde) to the branched (2-methylbutyraldehyde) product are determined.
    Example. Continuous hydroformylation of butene-1 was carried out as described in Example 6, using a catalyst precursor solution containing about
    300 ppm of rhodium, introduced as rhodium dicarbonylacetylacetonate, Texanol as solvent and about 11% by weight (about 80 molar equivalents of ligand per mole of rhodium) of a ligand of triphenylphosphine of the formula
    zoz snsnted
    the approximate composition of the catalyst and the average daily reaction rates (in gmol / l / h of the Sb-aldehyde product), as well as the molar ratio of linear (n-valeraldehyde) to pa3BetBAeHHOMy (2-methylbutyraldehyde) product are given in Table. 7 (test results - average daily).
    Froze Conducts continuous
    hydroformylation according to the method of Example 6, using a solution of a catalyst precursor containing about 300 ppm rhodium, introduced into
    of rhodium dicarbonyl acetylacetonate, Texanol as solvent, and about 12% by weight (about 80 molar equivalents of ligand per 1 mole of rhodium) of monosulfated triphenylphosphine. Your own ligand of formula
     SO iiHlCH,),
    The composition of the catalyst and the average daily reaction rates (in g-mol / l / h of Sat-aldehyde product), as well as the ratio of linear (n-valeraldehyde) to rupture (2-methylbuty 0 product are listed in Table 8 (average daily test results).
    PRI me R 9. Conduct hydroformylation of octene-1 for 9 days with continuous recycling of the liquid catalyst as follows.
    A liquid recycling reactor system is used, consisting of two 2.8 L stainless steel reactors equipped with agitation, connected to a battery, each containing a vertically mounted agitator and an annular tubular bubbler near the bottom of the synthesis gas feed reactor. The bubbler has a plurality of orifices of sufficient size to allow the flow of the desired gas into the liquid. The first reactor contains a shell with silicone oil as a means to bring the contents of the reactors to the reaction temperature, while the reaction solution in the second reactor is heated with an electric heater. Both reactors contain internal cooling coils for temperature control | reaction. The reactors are connected by a line to bypass any unreacted gases from the first reactor to the second, and also to part of the liquid reaction solution containing the aldehyde product and catalyst from the first reactor can be pumped to the second reactor, where the unreacted olefin from the first reactor is further hydroformed second reactor.
    Each reactor also has a pneumatic liquid level meter for automatic control of the liquid level in the reactor. In the first reactor, in addition, there is a line for introducing liquid olefin using a metering pump and a line for introducing synthesis gas through a bubbler, while the processed synthesis gas is fed into the second reactor along the same transmission line, which discharges unreacted synthesis gas. gas from the first reactor. In the second reactor there is also a blower; 1, | slang for the removal of unreacted gases. The line from the bottom of the second reactor is connected to the upper part of the evaporator in such a way that a part of the liquid reaction solution can be pumped from the second reactor to the evaporator. The evaporator is maintained under reduced pressure using a vacuum pump. Vaporized aldehyde free
    from non-volatile components of the liquid reaction solution of the separator part of the gas evaporator liquid. The remaining non-volatile catalyst contained in the liquid reaction solution is pumped back through the recycle line to the first reactor. There is also a pneumatic fluid level regulator on the recycle line. The vaporized aldehyde product is sent to water cooled.
    condenser, fluidized and collected in the receiver of the product.
    The hydroformylation reaction is carried out with a loading of about 0.779 liters of a catalyst precursor solution of dicarbonylacetylacetonate rhodium (approximately 300 ppm rhodium), approximately 23% by weight of the trioctylammonium salt of 3- (diphenylphosphine) benzene sulfonic acid of the ligand of the formula
    SO, NH (C8Hi,
    (about 120 molar equivalents of ligand per mole of rhodium) and about 77 May. % Cd-aldehydes as a solvent for the first reactor. Approximately 1.00 L of the same catalyst precursor solution is loaded into the second reactor. The reactor system is then purged with nitrogen to remove any available oxygen and the reactors are heated to their reaction temperature. Controlled streams of purified hydrogen and carbon monoxide are fed through a sparger into the first reactor and the pressure in the reactor is increased to operating pressure. When the liquid level in the first reactor starts to rise as a result of pumping liquid octene-1 and converting it into a liquid aldehyde product, part of the liquid reaction solution from the first reactor is pumped into the second reactor through the line in the upper part of the second reactor at a rate sufficient to maintain constant level in the first reactor. The pressure in the second reactor is increased to its operating pressure. The gas vented from the second reactor is analyzed and determined. The controlled stream of the processed synthesis gas (CO and Hz) is introduced: into the second reactor in order to maintain their desired partial pressure in the second reactor. Working pressures and reaction temperatures are maintained during hydroformylation. As the liquid level in the second reactor begins to rise as a result of pumping from the first reactor and the formation of a liquid aldehyde product. A portion of the liquid reaction solution is pumped to the evaporator separator at a rate sufficient to maintain a constant liquid level in the second reactor. The aldehyde product is separated at 125 ° C and at pressures of about 40 mm Hg. from the liquid reaction solution, condense and collect into the product receiver. The remaining non-volatile liquid reaction solution containing the catalyst is recycled back to the first reactor. Hydroformylation of said octene-; 1 is carried out continuously for 9 days. , -. Condition the reaction form. as well as the rate of formation of the aldehyde product (in g-mol / l / h) and the proportion. the direct aldehyde product to a branched (nonal to 2-methyl octane) is given in. 9. ... v.; EXAMPLE 10 Octe.a-1 hydroformylation was carried out for 9 days using a solution of a catalyst precursor of dicarbonylacetylacetonate rhodi (about 300 ppm rhodi), about ... 22.8 wt.% Ligand - trioctylammonium salt 3- (diphenylphosphine) -benzenesulfonyl C. lots (about 100 molar equivalents of l-; ganDan 1 mole of rhodium) and about 77 wt .: Cd-aldehyde as a solvent, and the procedure is carried out, hydroformylated as described in example 9. Samples of Sdaldehyde product; obtained on different continuous days: npouec ja, analyzed for atomic phosphorus and rhodium content using indirect plasma spectroscopy. The results are shown in Table. 10 .. The results show the practical absence of roDi and a very small amount of phosphorus in the aldehyde (nonanal) product ..: The proposed method, using the sulfonated phosphorus ligand of general formula (I), allows, in contrast to the known method, to carry out the hydroformylation process in a non-aqueous medium , which leads to a significant simplification of the stage of separation of target products and simplifies the technology of the whole process. Formula from the process of obtaining C4-C13-aldehydes by hydroformylation of C3-C12 olefins with carbon monoxide and hydrogen in the liquid phase at 70-120 ° C and a total pressure of 3.51-11.25 kg / cm with a molar ratio of CO : H2 2.5: 1-1: 20 in the presence of a soluble rhodium catalytic complex and a phosphorus ligand. And in the presence of a free sulfonated phosphorus ligand, with a quantity of 25-500 ppm and a molar ratio of ligand to rhodium.Yu. and in order to simplify the process technology, the process is carried out in a non-aqueous reaction medium using monoisobutyrate 2,2,4-trimethyl-1,3-pentadiol or aldehydes, which are target products, and / or by-products of liquid-phase condensation of aldehydes, which are formed directly in the hydroformylation process and have a boiling point above the temperature, as an organic solvent boiling of target aldehydes, and as a sulfonated phosphorus ligand use an organic soluble monosulfonated tertiary phosphine salt of the general formula where RI and R2 are taken together or separately but, -phenyl or cyclohexyl: an amine cation having the general formula. NKR3R4R5,; where Hz and R4 are taken together or separately, -CH3 or Rs is CeHi or Ci2H25, or CieH33.
    1715202
    11 Ta bl and c a 1
    Note, Reaction 1-3 and 5 reaction conditions: 100 ° C; 200 ppm rhodium, approximately 118 molar equivalents of ligand per mole of rhodium; 4.22 kg / cm; H2: CO: SyNb 1: 1: 1. In the experiment 4, the reaction conditions: 200 ppm rhodi: about 196 molar equivalents of ligand per millimeter, - 6.33 kg / cm: H2: CO: CsNb 1: 1: 1.
    e ch. n. e. Reaction conditions: 100 ° С; 200 ppm rhodium, about 20 molar equivalent of ligand per 1 mole of rhodi; 4.22 kg / cm: H2: CO: SzNb 1: 1: 1.
    Notes e. Reaction conditions:: 200 ppm rhode; - about 20 molar equivalents of ligand per mole of rhodium; 4.22 kg / cm; H2: CO: SzNb 1: 1: 1.
    , Table 2
    Table 3
    13
    Note. Reaction Conditions: 90 ° C; 200 ppm give birth, Changes in values reflect changes in daily
    14
    1715202 Table A, approximately 20 molar equivalents of ligand per mole of rhodium; 5.63 kg / cm; H2: CO 1: 1; 3.10 kg / cm butane-1.
    Table 5
    T a b l and c a level of liquid solutions in the reactor
     The incorrect function of the mass flow meter for monoxide carbon dioxide stopped the CO flow and prevented the formation of the aldehyde product. It was fixed and the reaction continued ...
     The incorrect function of the gas chromatograph prevented the precise determination of the molar ratio H / I, which led to questionable speed results. : Table 3
    t a b l and c a 7. ,
    权利要求:
    Claims (1)
    [1]
    Claim
    The method of producing Cd-Cp aldehydes by hydroformylation of C3-C12 a-olefins with carbon monoxide and hydrogen in the liquid phase at 70-120 ° C and a total pressure of 3.51-11.25 kg / cm 2 with a molar ratio of CO: H 2 2 , 5: 1-1: 20 in the presence of a soluble catalytic complex of rhodium and a phosphorus ligand and in the presence of a free sulfonated phosphorus ligand, with a rhodium amount of 25-500 ppm and a molar ratio of ligand to rhodium. 10200, and with the fact that, in order to simplify the process technology, the process is carried out in a non-aqueous reaction medium using Niemi as organic solvent monoisobutyrate '2,2,4-trimethyl-1,3-pentanediol or aldehydes, which are the desired products and / or byproducts razuyuschihsya directly during ·
    The above results show the practical absence of rhodium and a very small amount of phosphorus in the aldehydic (nonanal) product.
    The proposed method due to the use of sulfonated phosphorus boiling rounds above the boiling point of the target aldehydes, and as a sulfonated phosphoric ligand, an organic soluble monosulfonated tertiary phosphine tertiary salt of the general formula p K Pp / soX is used where Ri and R 2 taken together or separately are phenyl or cyclohexyl:
    M + is an amine cation having the general formula;
    NHR3R4R5, where R3 and R4 are taken together or separately, —CH3 or CsHtr;
    Rs - CeHi or Ci 2 H 2 5, or C1eNc.
    Table 1
    Experience Ligand (M + =) The reaction rate, g-mol / l / h The linear ratio of linear aldehyde: branched aldehyde 1 N + H (C 8 Hi 7 ) 3 0.42 4.2 2 N + H (CH 3 ) 2 (Cl 2 H 2 S) 0.31 6.5 3 N T H (SNsNSvZh ) 0.37 64 4 N + H (CH 3 ) 2 (C8H17) 0.29 8.6 5 N + H (CH3) 2 (Ci 6 H 33 ) 0.25 6.3
    Note. In experiments 1–3 and 5, reaction conditions: 100 ° C: 200 rpm of rhodium; approximately 118 molar equivalents of ligand per mole of rhodium; 4.22 kg / cm 2 ; L / CO. 'CsNb ^ = 1: 1: 1. In experiment 4, reaction conditions: 100 ° C: 200 ppm of rhodium; approximately 196 molar equivalents of ligand per. mole of rhodium; 6.33 kg / cm 2 ; H2: CO: CsNb = 1: 1: 1.
    Table 2
    ......... .... Experience Ligand (M + =) The reaction rate g-mol / / p! H The linear ratio of linear aldehyde: branched aldehyde 1 N + H (C 8 Hit) 31.95 1,57 2 N + H (CH 3 ) 2 (C12H 2 5) . 1,11 1.66
    N ote. Reaction condition: 100 ° C; 200 ppm of rhodium;
    'about 20 molar equivalents of ligand per 1 mol of rhodium; 4.22 kg / cm 2 ; H2: CO: CsNb = 1: 1: 1.
    Table 3
    Experience Ligand (M + =) ♦ The reaction rate g-mol / / l / h The linear ratio of linear aldehyde: branched aldehyde 1 N + H (C 8 Hi7) 30.82 1.13 2 N + H (CH3) 2 (C1 2 H25) 0.88 1.14
    Note: Reaction conditions: 100 ° C: 200 ppm of rhodium; 'approximately 20 molar equivalents of the ligand per 1 mol of rhodium; 4.22 kg / cm 2 ; H 2 : CO: CsNb = 1: 1: 1.
    Table 4
    Experience Ligand The reaction rate, g-mol / l / .h The linear ratio of linear aldehyde: branched aldehyde 1 TSGDFMS 11.62 2.543.77 1.73
    Note. Reaction conditions: 90 ° C; 200 ppm of rhodium, approximately 20 molar equivalents of the ligand per 1 mol of rhodium; 5.63 kg / cm 2 ; H2: CO = 1: 1; 3.10 kg / cm 2 butene-1.
    Table5
    Experience rrm Temperature ° C The molar ratio of the ligand. : rhodium 'Partial pressure Pound / inch 2Olefin dodesilt The reaction rate, g-mol / l / h Molar ratio linear alde guide branched alde guide With H 2
    1 25 100 10 222,5 0.53 3.2 2 25 100 10 22 99 5,0 1.37 3,7 3 200 120 200 22 44 5,0 3.76 11.8 4 500 70 fifty 22 44 5,0 0.93 13.9 5 200 100 1 s 110 40 5,0 2.04 16.7 6 200 100 100 100 40 5,0 2.88 5.1
    Table ^
    Work day Temperature ° C Rhodium *, rpm Ligand * May.% The partial pressure lb / in2Speed g-mol / l / h The linear ratio of linear aldehyde: branched aldehyde With 'V s 4 n 8
    0.9 85 261 13.05 21 58 2 0.75 7.43 1.9 83 264 13,2 18 56 3 1.82 9.42 3.0 70 269 13,4 17 57 3 1.32 9.29 3.9 70 278 13.9 17 57 3 1.27 9.28 4.8 70 287 14.3 17 57 3 1.211,07 9.41 6.0 70 296 14.8 18 58 3 11.41 6.8 70 249 12,4 thirteen 54 7 2.24 8.60 7.9 70 265 13,2 16 56. 6 2.03 9.73 9.0 83 289 14,4 16 56 6 1.81 10.33 9,4 '85 301 15.0 16 56 6 1.82 10.82 11.8 85 321 16.0 17 56 6 1,67 13.12 12.8 85 334 16.7 16 56 7 1.98 12.17 13.8 85 341 17.0 16 56 7 2.20 11.76 * Changes quantities reflect changes in the daytime level LIQUID solutions in the reactor
    Table7
    Work day Temperature ° C Rhodium,rrm Ligand, mas Partial Pressure Pound / inch 2Speed, g-mol / l / h The linear ratio of linear aldehyde: branched aldehyde WithC 4 H 8 1,0 85 254 9.7 16 56 6 1,04 20.89 1.7 85 255 9.3 fifteen 55 8 1.41 22.78 2.9 70 248 9.1 3 59 10 0.45 6.82 4.0 * 70 248 9.1 0 61 10 - - 4.8 * 70 248 9.1 0 60 10 - “· 6.0 70 311 11.4. 12 44 7 0.75 20.39 6.8 70 260 9.59.3 thirteen 56 8 1.66 22.01 8.0 70 256 fifteen 57 9 1,56 22.72 8.8 82 266 9.7 fifteen 57 9 1.40 22.42 9.4 8511.8 * 35 278 10,2 fifteen 60 9 1.28 25.69 294 10.8 16 64 9 0.81 - 12.8 * 85 309 11.3 16 57 10 0.79 13.7 * 85 303 11.1 16 57 12 0.68 -
    The wrong function of the mass flowmeter for carbon monoxide stopped the CO supply and prevented the formation of the aldehyde product. She was recorded and the reaction continued.
    ** The incorrect function of the gas chromatograph prevented the accurate determination of the molar ratio N / I, which led to dubious results in speed.
    Table 8
    Day Temperature, ° C you
    rhodium; ppm
    Ligand wt.%
    ^ The partial pressure lb / in2
    Speed, g mol / l / and
    With
    H 2
    C 4 n 0
    Linear product: branched product molar ratio
    1,0 85 275 10.9 fifteen 56 7 1.46 2.0 83 260 10,4 fifteen 56 8 1.78 3.0 70 266 10.6 fifteen 56 8 1,62 4.0 70 276 10.9 fifteen 56 8 1,54 4.8 70 285 11.5 16 56 8 1,53 5.8 70 290 11.6 fifteen 56 9 1,61 6.8 70 295 11.8 fifteen 56 9 1,57 8.0 80 300 12.0 fifteen 56 9 1,60 9.0 82 304 12.1 fifteen 55 10 1,64 9,4 85 309 12.3 10 51 fifteen 2.86 11.8 85 309 12.3 8 49 14 4.34 12.6 85 435 17.4 16 55 eleven 2.23
    16.91
    16.79 19.03
    21.59
    21.80 21.98 22.45
    22.60 22.18 12.63 474
    8.15
    17 1715202 4th
    Τ a b l c a 9
    Reaction rates Days operations 2 n 1 9 The supply of octene-1, mol.%: 0cten-1 98.28 98.28 98.28 0cten-2 1,54 1,54 1,54 Octane 0.17 0.17 0.17 The first reactor:Temperature ° C 80.5 80,4 80.5 Pressure lb / in 291.2 91.7 91.7 H 2 lb / in 270.6 67.9 83.0 CO, lb / in 2 0cten-1, mol.% 16.59.0 20.79.8 6.38.8 0cten-2, mol.% 4.1 2.6 4.9 The second reactor: Temperature ° C 90,4 90,4 90.6 Pressure lb / in 282.7 84.7 83.7 H 2 lb / in 254.9 62,4 75.0 СО, pound / inch 225,4 19.3 6.0 0cten-1, mtd 1,0 1,2 1,2 Octen-2, pier 3.3 2,3 4,5 Results: C ^ -Aldehydes, g mol / l / h 1.16 1.14 1,07
    The ratio of linear aldehydes: branched
    aldehydes 6.3 5.5 12.3 T a b faces 10 Day of operation | phosphorus, rpm 1 Rhodium, ppm 3 8.8 1 5 22.0 1 6 25.0 1 9- 22.0
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    GB2193494B|1991-01-02|
    DK359987D0|1987-07-10|
    KR910008369B1|1991-10-12|
    ZA875058B|1988-03-30|
    AT74120T|1992-04-15|
    CN1020720C|1993-05-19|
    CS527687A2|1990-02-12|
    PL151795B1|1990-10-31|
    NO165877C|1991-04-24|
    FR2603579B1|1990-05-25|
    FI89351C|1993-09-27|
    US4716250A|1987-12-29|
    NO165877B|1991-01-14|
    GB2193494A|1988-02-10|
    DK359987A|1988-01-11|
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    法律状态:
    优先权:
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    US06/884,197|US4716250A|1986-07-10|1986-07-10|Hydroformylation using low volatile/organic soluble phosphine ligands|
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