Method of producing aldehydes c sub seven

专利摘要:
In the prodn. of aldehydes by reacting olefins with CO and H2 in the liquid phase in the presence of water and water-soluble Rh-phosphine complex cpds. (I) at 20-150 deg.C and 1-200 bar (100- 20 x 10 power 3 kPa), (I) contg. trisulphonated or tricarboxylated triarylphosphones (II) are used as catalyst and the reaction medium contains a solvent promoter (III). Pref. (II) is of the formula P(Ar1(X1M)(Y1n1))(Ar2(X2M)(Y2n2)) (Ar3(X3M)(Y3n3))(IIA): Ar1, Ar2 and Ar3 = phenyl or naphthyl gps.; esp. phenyl; Y1, Y2 and Y3 = linear or branched 1-4C alkyl, alkoxy, halogen, OH, CN, NO2 or R1R2N- gps.; R1 and R2 = linear or branched 1-4C alkyl; X1, X2 and X3 = a carboxylate (COO-) and/or sulphonate (SO3-) gp.; esp. a sulphonate gp.; n1, n2 and n3 independently = 0-5; M = an alkali alkaline metal, Zn, NH4 or quat. ammonium of the formula N(R3R4R5R6)+; R3, R4, R5 and R6 = linear or branched 1-4C alkyl.
公开号:SU1428188A3
申请号:SU853867686
申请日:1985-03-20
公开日:1988-09-30
发明作者:Барманн Гельмут；Корнильс Бой；Конколь Вернер；Липпс Вольфганг
申请人:Рурхеми Аг (Фирма)；
IPC主号:

专利说明:


s
This invention relates to a process for the preparation of higher aldehydes by hydroformylation of olefins.
The aim of the invention is to increase the conversion and productivity of the process.
Example 1 A, For the preparation of a catalyst, a 1 liter autoclave equipped with an immersion nozzle is fed with 345 MP of an aqueous solution of trisodium-tri (m-sulfophenyl) phosphine with a salt content of 0.4% by weight and with 40U ppm as an acetate give birth, and then feed synthesis gas (volume ratio co / 1: 1) under a pressure of 25 bar (2.5 1U kPa). Then reaction-. After stirring for 3 hours, the mixture is treated with synthesis gas to form an active catalyst. After cooling (until the stirring is stopped, after 15 minutes, the excess solution (g) through the immersion nozzle is removed and analyzed. The remaining solution remains in the autoclave.
B. For hydroformylation, 9.75 g (2.5 wt.%) Of tetradecyltrimethylammonium methasulfate was added to the solution obtained according to step A, and 170 g of n-hexene-1 was added while stirring. At a constant pressure of 25 bar (2.5-1u kPa), the mixture is heated to 125 ° C and left at this temperature for 3 hours. Then the mixture is cooled to and settled. The upper organic phase through the immersion nozzle is removed, weighed and examined by gas chromatography.
The results of Example 1 are summarized in Table 1 (given values for activity and productivity refer to the quantities of the aqueous and organic phases present in the autoclave. The specific gravity of the aqueous phase is 1.171).
Examples 2-13 illustrate the effect of various dissolution agents. The results of the capping of the th example are the average values of five hydroformylations using the same catalyst solution (see Table 2 and 3).
In Examples 14-29, water soluble trisulfonated phosphine is reduced. to the extent that the three (m-sulfophenyl) f6sphine sodium salt content is 12.2% by weight. For the rest, Example 1 is repeated. Results at 0
0
five
0
five
0
five
0
five
Measures 14-29 (see Tables 4 and 5) also represent the mean values of five hydroformylations using the same catalyst solution.
Example 30. Example 1 is repeated, with the difference that the reaction is carried out at.
The results of the experiment are summarized in table 6.
PRI m e r 31. Example 1 is repeated, with the difference that the reaction is carried out at.
The results of the experiment are summarized in table 7.
Example 32. Example 1 is repeated, with the difference that the reaction is carried out under a pressure of 15 bar.
The results of the experiment are summarized in table 8.
EXAMPLE 33. Example 1 is used, with the difference that the reaction is carried out under a pressure of 30 bar.
The results of the experiment are summarized in table.
EXAMPLE 34 Example 1 is repeated, with the difference that n-octene, n-decene and n-tetradecene are used as the olefin.
The results of the experiment are summarized in Table 10- (the results of each experiment represent the average of five hydroformylations using the same catalyst solution).
Comparative example 1 (prototype). Example 3 is repeated, with the difference that instead of lauryl trimethyl ammonium chloride, lauryl trimethylammonium bromide is used. The following results are obtained (average values of five hydroformylations):
Conversion% 19
Activity, mole
aldehydes C- / g-atom
give birth -min1,25
Performance,
g aldehyde C: f / CM
catalyst solution.h 0.037
Comparison of the results of example 3, summarized in Table 2, with the results of this example shows the advantage of the proposed method over the known one.
Comparative example 2 (prototype). Example 32 is repeated, with the difference that lauryltrimethylammonium bromide is used instead of tetradecyltrimethylammoxy methasulphate. The following results are obtained (average values of five hydroformylations):
Conversion,%
Activity, mol of aldehydes Cj / g-atom rhodium, min Performance, g aldehydes of catalyst solution-h
Comparison of the results of example 32, shown in table 8, with the results of this example shows the advantage of the proposed method over the known.
Comparative example 2 (prototype) Example 33 is repeated, with the difference that, instead of metasulfate tetradec-trimethylammonium, lauryltrimethylammonium bromide is used. The following results are obtained (average values of five hydroformylations):
Conversion% 40
Activity, mole
aldehydes With / g-atom
give birth .min2,61
, Performance,
g aldehyde C-J / CM
catalyst solution-h 0.069
Comparison of the results of example 33, summarized in table 9, with the results of this example shows the advantage of the proposed method over the known.
Comparative example 4 (prototype). Example 34 is repeated with the difference that lauryltrimethylammonium bromide is used instead of tetradecyltrimethylammonium metasulfate.
The results obtained are summarized in Table 11 (average values of five hydroformylations).
88: 4
Comparison of the results of example 34 (see table 10) with the results of this example shows the advantage of the proposed method over the known one.
Thus, the use of these additives can increase the conversion and productivity of the process.

权利要求:
Claims (1)
[1]
Invention Formula
The method of producing aldehydes C, - Cifs by reacting the corresponding olefin with carbon monoxide and hydrogen in the liquid phase at a temperature of 115-130 ° C and a pressure of 15-20 bar in the presence of water, give rise to the form of a triphenylphosphine triphosphate as a catalyst and a dissolution agent, followed by a spin for the purpose of increasing the conversion and productivity of the process, 1-5% of the mass of the aqueous solution of the compound selected from the group comprising the tetradehyde;
mony, oleic alcohol, polyglycol with mol.m. 200, triethylene glycol, sodium salt of oleic acid and tetramethylene sulfone.
Table 1
C :) n
:
WITH:; Ali
23.2
1.43 0.045
25
27
.1,58 1,74 0,049 0,054
Note. As a dissolution agent in example 2, use
oleic alcohol, in example 3 - lauryl trimethyl ammonium chloride, in example 4. - lauryl pyridinium chloride, in example 5 - benzyl trimethyl ammonium sulfate, in example 6 - dodecyl trimethylammonium sulfate, in example 7 - benzyl trimethylammonium ammonium sulfonate, in example 6 - benzyl trimethylammonium ammonium sulfonate, in a sample of 5 - benzyl trimethylammonium ammonium chloride, in benzyl trimethylammonium sulfate ammonium chloride, in benzyltrimethylammonium chloride;
thirty
thirty
35
33
1.88 2.28 2.41 2.36
0.056 0.069 0.072 0.071
Conversion according to gas chromatography,%
Activity,
mole aldehyde C-atomic rhodi-min
MOJ g
Productivity, g grams aldehyde CMCZ-catalyst solution h
Note.
Tetradecyltrimethylammonium meta-sulfate was used as a solution in Example 9, benzyltrimethylammonium sulfate was used in Example 10, dodecyltrimethylammonium methasulfonate was used in Example 10, and benzyltrimethylammonium methaculphonate in dimethymethymethylmethylomethylammonium was used as dissolution in benzyl trimethyl ammonium.
That blitz4
Conversion according to gas chromatography.
Activity,
mole aldehyde C
Noted
As the dissolution agent in example 14, polyglycol with mol.m. 200, in example 15 - trimethylhexadecylammonium bromide, in example 16 - triethylene glycol, in example 17 - sodium salt of oleic acid, in example 18 - tetramethylene sulfone, in example 19 - tributylhexadecylammonium lactate.
25
26
28
27
1.59
1.63
0.0500.051
1.81 1.75 0.059 0.053
86
43.5
39
42 50
Conversion on gas chromatography,%
The ratio of n / i-aldehyde
Organic phase, g Aqueous phase in the reactor, g
Activity,
 . Aldehyde C 1 g-atom rhodium-min J
Performance, g grams of aldehydes C
28
23
ST
29
37
31
97/398/2 97/397/397/397/3
160153 166173175165
395 394-384370370383
1,421.12 1,951,702,191.68
0,0440,036 0,0610,0530,0680,052
Conversion on gas chromatography,%
The ratio of n / i-aldehydes
Organic phase, g Aqueous phase in the reactor, g
Activity,
Aldehyde C 1 lF atom of rhodium - min j
50
43
49
57
52
50
Performance, grams of aldehydes C
see the setting of the catal | congestion. h
95/596/495/5 95/595/595/5
183191210201197196
f
394374371371368376
2,912,753,483,873,493.30
0.0910.0860.1080.12210.1090.103
ST
29
37
31
49
57
52
50
Conversion on gas chromatography,%
The ratio of n / i-aldehydes
Organic phase, g Aqueous phase in the reactor, g
Activity,
mole aldehyde
21
18
21
20
23
21
98/298/298/298/297/398/2
168165165167167166
394390375374372381
1,120,951,161,12 1,291,13
Conversion on gas chromatography,%
The ratio of n / i-aldehyde
Organic phase, g Aqueous phase in the reactor, g
48
50
56
42
49 49
Activity,
mol aldegdov With -atat roDi mi} 1
lr rior
MOJ Mr. SN
Performance,
I P 1: VD - j I cm of a solution of the catalyst - h J
95/5 95/5 94/695/595/595/5
205 212 190197218204
0
374 368 365365360366
3.30 3,662,843,723,43
0,103 0,112 0,1140,0880,1160,107
21
20
23
21
50
56
42
49 49
Parameters n-octen n-dotsen n-tetradecene
Conversion of gas chromatography,% 46.2 27.622.9
The ratio of n / i-aldehydes 91/9 89/11 86/14
Activity,
G mole of aldehydes SL2,241,350,63
Lr-Atrm Rodi Min J
Performance,
(grams of aldehydes C P 0.082. 0.055 0.037 cm of a solution of catalysac tora j
Table 11 Parameters inn-octen 1 n-Detsen n-Tetradecene
Conversion, gas chromatography,% 40,822,418,6
The ratio of n / i-aldehydes 89/1188/12 84/16
Activity,
G mole of aldehydes CL1,921,090,46
L g-atom rhodium -min J
Performance,
G grams of aldehydes With 1 0,0610,038 0,019
I cm solution ca. tapi (mash h J
Compiled by R. Margolin Editor M. Kelemesh Tehred A. Kravchuk Proofreader N. Korol
Order 4869/58 Circulation 370 Subscription
VNIIPI USSR State Committee
for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
„, ......, - .-“ ----..- ------------------------------ -
Production and printing company, Uzhgorod, st. Project, 4

类似技术:

---

公开号 | 公开日 | 专利标题

---

SU1428188A3|1988-09-30|Method of producing aldehydes c sub seven - c sub fifteen

---

US4399312A|1983-08-16|Catalytic process

---

Tundo et al.1989|Gas-liquid phase-transfer catalysis: a new continuous-flow method in organic synthesis

---

PL151795B1|1990-10-31|Hydroformylation using low volatile/organic soluble phosphine ligands.

---

CN1185784A|1998-06-24|Synthesis of and hydroformylation with fluoro-substituted bidentate

---

US4593126A|1986-06-03|Process for preparing aldehydes

---

PL149283B1|1990-01-31|Method of recovering rhodium from oxo-synthesis reaction products

---

US6051743A|2000-04-18|Process for the preparation of predominantly unbranched higher primary alcohols

---

US4460786A|1984-07-17|Process for the selective addition of a compound having an activated carbon atom onto a substituted conjugated diene

---

FR2485518A1|1981-12-31|PROCESS FOR THE PRODUCTION OF ETHYLENE GLYCOL AND ITS CARBOXYL ESTERS BY CATALYTIC HYDROGENATION OF GLYCOLALDEHYDE

---

Hayashi et al.1977|Palladium | assisted alkylation of olefins with stabilized carbanions

---

US4879418A|1989-11-07|Process for the preparation of aldehydes

---

US5274183A|1993-12-28|Water-soluble sulfonated diphosphines

---

US4382148A|1983-05-03|Process for the preparation of glycol aldehyde

---

US6156936A|2000-12-05|Hydroformylation of olefin feeds containing dienes

---

EP0158518B1|1991-07-10|Process and accompanying catalysts for the hydroformylation of formaldehyde to glycol aldehyde

---

CA1162542A|1984-02-21|Catalytic asymmetric hydrogenation

---

US3609180A|1971-09-28|Process for preparing carboxylic acid esters of unsaturated alcohols

---

EP0087298B1|1986-05-28|Process for producing benzaldehydes

---

GB2451325A|2009-01-28|Hydroformylation process

---

JPH06293692A|1994-10-21|Preparation of aldehyde

---

JP2501668B2|1996-05-29|Method for producing amines

---

EP0072051B1|1984-11-07|Process for the preparation of glycol aldehyde

---

EP0019960B1|1983-11-09|Preparation of 3,7-dimethylocta-1,7-diene

---

US7098369B2|2006-08-29|Process for the production of primary alcohols

同族专利:

---

公开号 | 公开日

---

CS248736B2|1987-02-12|

---

DE3586466D1|1992-09-17|

---

HUT39705A|1986-10-29|

---

PL252603A1|1986-02-25|

---

EP0157316A3|1987-05-27|

---

ZA852318B|1985-11-27|

---

HU199381B|1990-02-28|

---

BR8501525A|1985-11-26|

---

DE3412335A1|1985-10-10|

---

AT79367T|1992-08-15|

---

EP0157316A2|1985-10-09|

---

JPS60224651A|1985-11-09|

---

RO92611A|1987-09-30|

---

KR850008480A|1985-12-18|

---

AU4083385A|1985-10-10|

---

ES8603167A1|1985-12-16|

---

KR880001352B1|1988-07-28|

---

AU578085B2|1988-10-13|

---

EP0157316B1|1992-08-12|

---

ES541534A0|1985-12-16|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

GB708441A|1951-05-23|1954-05-05|Standard Oil Dev Co|Synthesis of oxygenated organic compounds|

---

FR62634E|1952-03-20|1955-06-15|Ruhrchemie Ag|Process for the catalytic fixation of water gases on unsaturated hydrocarbons|

---

US4248802A|1975-06-20|1981-02-03|Rhone-Poulenc Industries|Catalytic hydroformylation of olefins|

---

FR2314910B1|1975-06-20|1977-12-02|Rhone Poulenc Ind|

---

GB2085874B|1980-09-04|1984-08-08|Johnson Matthey Plc|Hydroformylation of olefins|

---

DE3234701A1|1982-09-18|1984-04-05|Ruhrchemie Ag, 4200 Oberhausen|METHOD FOR PRODUCING ALDEHYDES|DE3534314A1|1985-09-26|1987-04-02|Ruhrchemie Ag|METHOD FOR PRODUCING ALDEHYDES|

---

US4716250A|1986-07-10|1987-12-29|Union Carbide Corporation|Hydroformylation using low volatile/organic soluble phosphine ligands|

---

US4825003A|1986-09-17|1989-04-25|Mitsui Toatsu Chemicals, Incorporated|Production process of 2-chloropropionaldehyde|

---

US4731486A|1986-11-18|1988-03-15|Union Carbide Corporation|Hydroformylation using low volatile phosphine ligands|

---

IT1229512B|1989-01-27|1991-09-03|Eniricerche Spa|PROCEDURE FOR CATALYTIC HYDROFORMILATION DI.OLEFINE|

---

US5215667A|1991-08-20|1993-06-01|Exxon Chemical Patents Inc.|Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction|

---

US5288818A|1991-08-20|1994-02-22|Exxon Chemical Patents Inc.|Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction|

---

DE4210026A1|1992-03-27|1993-09-30|Hoechst Ag|Decyl alcohol mixtures, phthalic esters obtainable therefrom and their use as plasticizers|

---

DE4330489A1|1993-09-09|1995-03-16|Hoechst Ag|Process for the hydroformylation of butadiene-1,3|

---

DE4427428A1|1994-08-03|1996-02-29|Basf Ag|Process for the preparation of aldehydes|

---

DE4440552A1|1994-11-12|1996-05-15|Hoechst Ag|Process for the preparation of formyl carboxylic acid esters|

---

FR2729385B1|1995-01-17|1997-04-04|Centre Nat Rech Scient|PROCESS FOR HYDROFORMYLATION OF AN OLEFIN IN A BIPHASIC MEDIUM|

---

DE19700805C1|1997-01-13|1998-08-06|Hoechst Ag|Process for the preparation of aldehydes by hydroformylation of olefinic compounds with 3 to 5 carbon atoms in the presence of an aqueous phase containing rhodium and sulfonated triarylphosphines as catalyst|

---

DE19700804C1|1997-01-13|1998-08-06|Hoechst Ag|Process for the preparation of aldehydes by hydroformylation of olefinic compounds with 6 to 16 carbon atoms in the presence of an aqueous phase containing rhodium and sulfonated triarylphosphines as catalyst|

---

DE19957528A1|1999-11-30|2001-05-31|Oxeno Olefinchemie Gmbh|Hydroformylation of olefin to aldehyde, used e.g. for producing alcohol or carboxylic acid or in aldol condensation, involves multiphase reaction in tubular reactor with catalyst in solvent phase and olefin in disperse phase|

---

FR2813305B1|2000-08-23|2004-02-13|Inst Francais Du Petrole|IMPROVED HYDROFORMYLATION PROCESS USING A COBALT AND / OR RHODIUM-BASED CATALYST IN A NON-AQUEOUS IONIC SOLVENT|

---

DE102005019237B4|2005-04-26|2008-11-20|Oxea Deutschland Gmbh|Process for the hydroformylation of substituted allylbenzenes|

---

GB0616486D0|2006-08-21|2006-09-27|Univ St Andrews|Chemical process|

---

DE102008044783B4|2008-08-28|2012-05-16|Oxea Gmbh|Process for the recovery of aliphatic C3 to C10 aldehydes from high boilers by thermal treatment|

---

DE102009004655B4|2009-01-15|2013-02-14|Oxea Gmbh|Process for the preparation of aldehydes|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

DE19843412335|DE3412335A1|1984-04-03|1984-04-03|METHOD FOR PRODUCING ALDEHYDES|

---