前苏联专利SU1537133A3 Method of producing aldehydes c4-c11

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专利摘要:
Transition metal-bis-phosphite catalyzed carbonylation processes, especially hydroformylation, as well as transition metal-bis-phosphite compositions, bis-phosphite ligands and transition metal-bis-phosphite catalysts.
公开号:SU1537133A3
申请号:SU864028173
申请日:1986-09-04
公开日:1990-01-15
发明作者:Биллиг Эрнст；Джордж Абатджоглоу Энтони；Роберт Брайант Дэвид
申请人:Юнион Карбид Корпорейшн (Фирма)；
IPC主号:

专利说明:

The invention relates to an improved method for producing aldehydes by the hydroformylation method.
The purpose of the invention is to increase the sec-, lektivnosti process on n-aldehyde.
Example 1. A series of different solutions of precursor rhodium complex catalysts, consisting mainly of rhodium dicarbonyl-acetylacetonate and various bis-phosphite ligands, are prepared and used to hydroformylate butene-1 to aldehydes containing 5 carbon atoms of atomic carbon.

s
Rhodium dicarbonylacetylacetonate is mixed at room temperature with various bis-phosphite ligands having the following formula:
OCHA
(SEDs
CH30
CH30 CH30
with
SSNg) 3
where each of Z is the radical presented in table 1,
and a solvent to produce various catalytic precursor solutions containing those listed in Table. 1 number of parents and ligands.
Each rhodium catalytic precursor solution thus obtained is then used to hydroformylate butene-1 in a stainless steel autoclave with a magnetic stirrer having a capacity of 100 ml. A gas distributor is used to introduce gases at the desired partial pressure. The autoclave is also provided with a pressure sensor for determining the reaction pressure with an accuracy of + 0.0007 atm and a platinum resistance thermometer for determining the temperature of the solution in the reactor with an accuracy of ± 0.1 ° C. The reactor is subjected to external heating using two 300 W heating panels. The temperature of the solution in the reactor is controlled by a platinum resistance bensor connected to an external temperature controller to control the temperature of the external heating heaters.
Each time the hydroformylation reaction is carried out, approximately 15 ml (about 14 g) of the obtained rhodium catalytic precursor solution under nitrogen atmosphere is charged to the autoclave reactor and heated to the reaction temperature used (see Table 1). The reactor is then pumped out to approximately 0.35 atm and 2.5 ml (about 1.5 g) of butene-1 are introduced into it, then carbon monoxide and hydrogen are introduced into the reactor through a gas distributor (partial pressures are presented in Table 1) and wire t, hydroformylation of trans-butene 1.
The rate of the reaction of hydroformylation, expressed in moles of aldehydes obtained containing 5 carbon atoms, 1 atoms per liter, is measured by successive pressure drops to atm in the reactor, taking into account the nominal operating pressure in the reactor, and molar linear relationship
The product (n-valerian aldehyde) to the branched (2-methyl aldehyde) is determined gas chromatographically. The data presented in Table. 1, with specified results
5 was obtained by measurement carried out after the conversion of approximately 5-20% of the original butene-1.
Example 2. The procedure and conditions of Example 1 are used to prepare a series of rhodium catalytic precursor solutions using rhodium dicarbonylacetylacetonate, a solvent, and various bisphosphite ligands having the following formula:
o-z
five
five
s (sn3b
where each. of Z is the radical indicated
in tab. 2,
and hydroformylation of butene-1 is reproduced, replacing butene-1 with propylene using a composition of pre-mixed gases of carbon monoxide, hydrogen and propylene after adjusting the reaction pressure to 1.4 atm.
5 with nitrogen and varying the precursor solution of the rhodium complex catalyst and the conditions of the hydroformylation reaction, as shown in Table. 2. Determine the reaction rate of the hydroforming miling, expressed in mol / l / h of the resulting oil aldehyde, as well as the molar ratio of the linear product (n-butyraldehyde) to the branched product (iso-butane aldehyde). Results
are presented in table. 2
Example 3. The procedure and conditions of example 1 are used for semi-CH30 CH30.
51
a rhodium catalytic precursor solution using rhodium dicarbonylacetylacetonate, a valeric aldehyde trimer as a solvent and a bis-phosphite ligand of the following Formula:
SNЈT
: (sn3) 3
/ O- -SDNY
with
(sns) 3
and reproduce butene-1 hydroformylation using various olefins as a starting material for hydroformylation, varying the solutions of the rhodium complex catalyst precursor and the hydroformylation reaction conditions (see Table 3). The reaction rate of hydroformylation, expressed in mol / l / h of the resulting aldehyde, as well as the molar ratio of the linear aldehyde to the branched aldehyde product, as determined analogously to Example 1, are presented in Table. 3
Example 4. The procedure and conditions of Example 1 are used to prepare a rhodium catalytic precursor solution using rhodium dicarbonylacetylacetonate, a valeric aldehyde trimer as a solvent and a bis-phosphite ligand of the following formula:
(CH & (CH3) 3
(svdz X JL D (sn3) (sne) 3 Chsnyss-on ochGo)
G / O / R
(sns
C (CH3) 3
and reproduce hydroformylation of butene-1 using a precursor solution of a rhodium complex catalyst and the following reaction conditions of hydroformylation; the reaction rate of hydroformylation is 5.7 mol / l / h based on the resulting aldehydes containing 5 carbon atoms, and the molar ratio of linear n is valeric aldehyde to branched 2-methylaldehyde product, defined analogously to example T, is equal to
0
one
336
Precursor solution and reaction conditions: 250 ppm rhodium; 2 wt.% Bis-phosphite ligand (7.7 mol of bis-phosphite ligand per 1 mole of rhodium) .; 70 C, 5 atm CO: H2 (molar ratio 1: 2) Ј 2.45 atm of butene-1.
Example 5. Using the procedure and conditions of example 2, a rhodium catalytic precursor solution is obtained using rhodium dicarbonyl acetylacetonate, valeric aldehyde trimer as solvent and bis-phosphite ligand of the following formula:
(Ш3) з (СНзЪ
rsk
C (CH3) 3
o-to)
h2h
(SNG
С (СН3) 3С (СН3) 3С- (СН3) 3С-
C (CH3) 3 and reproduce hydroformylation
propylene using a solution of a rhodium complex catalyst precursor and the following hydroformylation reaction conditions: the hydroformylation reaction rate is 1.06 mol / l / h based on the resulting oil aldehyde, and the molar ratio of linear n-butyraldehyde to branched isomas nous aldehyde equal to 21.6.
Precursor solution and reaction conditions: 250 ppm rhodium, 4 mol of bis-phosphite ligand per 1 mole of rhodium; 70 ° С, 6.3 atm СО: Н: propylene (molar ratio 1: 1: 1).
Example 6. The procedure and conditions of Example 2 are used to prepare a solution of a precursor of a rhodium catalyst using rhodium dicarbonylacetylacetonate, a valeric aldehyde trimer as a solvent, and a bis-phosphite ligand of the following formula:
) -SeN, 9
and reproduce propylene hydroformylation using solutions
precursors of a rhodium complex catalyst and hydroformylation reaction conditions. The results of determining the reaction rate of hydroformylation, expressed in mol / l / h based on the resulting oil aldehyde, and the molar ratio of linear n-oil aldehyde to branched isobutyraldehyde in the resulting product are presented in Table. four.
In experiments 1-4 tab. Figure 4 shows the effect of different partial pressures of carbon monoxide on the course of the reaction in experiments 5-11 — the effect of different concentrations of bis-phosphite ligand on the process; in experiments 12-16, the effect of the reaction temperature on the reaction.
Example 7. The procedure and procedure of example 1 is used to prepare a solution of a precursor of a rhodium catalyst using rhodium dicarbonylacetylacetonate, a solvent and a bisphosphite ligand, and the butaten-1 hydroformylation is performed using various bisphosphite ligands of the following formula:
(СЗДз С
XP-0-W-0-P
/
ABOUT
where W is divalent bridging
Group.
Solutions of the precursor of the rhodium complex catalyst and the results of determination of the reaction rate of hydroforming, carried out analogously to Example 1, expressed in mol / l / h based on the aldehydes C obtained (pentanali) and the molar ratio of linear n-valerian aldehyde to branched 2-methyl methyl - mu aldehyde are presented in table. five.
Precursor solution and reaction conditions: 250 ppm rhodium; 2 wt.% Bis-phosphite ligand; 70 ° C
7 atm CO: H (molar ratio 1: 2); 2.5 ml of 1-butene (2.45 atm of 1-butene)
In experiment 1, the solvent is valeric aldehyde trimer, and in
71338
max 2 and 3 - hexanol 2,2,4-trcmethyl -1 -1E-pentadiol monoisobutyrate.
Example 8. The procedure and conditions of Example 2 are used to prepare a solution of a precursor of a rhodium catalyst using rhodium dicarbonylacetylacetonate, a solvent and a bis-phosphate ligand and reproduce propylene hydroformylation using various bis-phosphite ligands of the following formula:
ten
15
FNZ) e
Chu
about /
P-0-W-0-P.
sg o
0
five
0
five
0
five
50
55
(Shz
where W is divalent bridging
Group.
The solutions of the precursors of the rhodium complex catalyst, the specific rates of the hydroformylation reaction, expressed in mol / l / h based on the resulting oil aldehyde, and the molar ratio of the linear product (n-oil aldehyde) to the branched product (isomaldehyde) are listed in Table . 6
Precursor solution and reaction conditions; 250 ppm rhodi Ј 4 mol of bis-phosphite ligand per 1 mole of rhodium; 70 ° С, 6.3 atm CO: Ng: propylene (molar ratio 1: 1: 1).
In Test 1, the solvent is valeric aldehyde trimer, in Test 2 and 3, Texanol.
Example 9. Continuous hydroformylation of butene-1 using a bis-phosphite ligand is carried out as follows.
The hydroformylation is carried out in a glass reactor operating according to the principle of continuous hydroformylation by passing the bute-1 one-time through. The reactor is a 90 ml wall flask immersed in an oil bath with a glass viewing window. Using a syringe, approximately 20 ml of a freshly prepared solution of the rhodium catalyst precursor is charged into the reactor after purging
Nitrogen systems. The precursor solution contains approximately 250 ppm of rhodium, administered as a rhodium dicarbonyl acetylacetonate, about 2 wt.% Bis-phosphite ligand of the following formula:
(CH &
CCH &
(about 8.0 mol of ligand per 1 mol of rhodium) and texanol as a solvent. The reactor is closed, the system is purged with nitrogen again and the oil bath is heated on the burner to the desired hydroformylation reaction temperature. The hydroformylation reaction is carried out at a total gas pressure of approximately 11.2 atm, where the partial pressures of hydrogen, carbon monoxide and butene-1 correspond to the values given in Table. 7 and the remainder is nitrogen and aldehyde product. Flows of feed gases (carbon monoxide, hydrogen, butene-1 and nitrogen) are controlled individually using flow meters. The feed gases are dispersed in the precursor solution through glass bubbler filters. Reaction temperatures are given in table. 7. The flow of unreacted feed gas carries away the aldehydes C5 produced and the outgoing gas is analyzed for approximately 5 days of continuous operation. The approximate daily values of the reaction rate, expressed in mol / l / h, based on the resulting C5 aldehydes, and the molar ratio of the linear product (n-valeric aldehyde) to the branched product (2-methyl aldehyde) are presented in Table. 7
Example 10. Butene-1 is hydroformed in the same way as Example 9 using the following bis-phosphite ligand. Formulas: H3CO OCH3
(f-L fa
lCH3) jC- X4 $ J-C (CH3) 3 sNH CHjO OV-Ov, 0 (L)
ten
15
20
25
0
five
0
five
0
The hydroformylation is carried out in a glass reactor operating on the principle of continuous hydroformylation by passing one butene-1. The reactor consists of a 90 ml thick-walled bottle immersed in an oil bath with a glass window for observation. After flushing the system with nitrogen, approximately 20 ml of a freshly prepared solution of the rhodium catalyst precursor is loaded into the reactor with a syringe. The precursor solution contains about 250 ppm of rhodium, administered as rhodium dicarbonylacetylacetonate, approximately 2.0 wt.% Bis-phosphite ligand (about 8.3 mol of ligand per mole of rhodium) and hexanol as a solvent. After sealing the reactor, the system is again purged with nitrogen and the oil bath is heated by a burner to the desired hydroformylation reaction temperature. The hydroformylation reaction is carried out at a total gas pressure of approximately 11.2 atm. The partial pressures of hydrogen, carbon monoxide and butene-1 are listed in Table. 8. The remainder is nitrogen and aldehyde product. The feed gas streams (carbon monoxide, hydrogen and butene-1) are individually controlled using flow meters and the feed gases are dispersed in the precursor solution using glass filter bubblers. Reaction temperatures are given in table. 8. The flow of unreacted feed gases carries away the aldehydes C produced and the outgoing gas is analyzed for approximately 5 days of continuous operation. Table 8 shows the approximate average daily values of the reaction rates expressed in mol / l / h based on the resulting C5 aldehydes and the molar ratio of linear n-valeric aldehyde to branched 2-methyl aldehyde.
Example 11. Butene-2 (ratio of cis- and trans-isomers of butene-2 approximately 1: 1) is hydroformylated as in Example 9 using the bis-phosphite ligand of the following formula: (ru., NesO OCHN
five
(svdz
CH30-CH30- ((cHj;
F-41
C (SNSCH3
° - pX§ -C9HS - § -С9На
ten
15
111537133
The hydroformylation is carried out in a glass reactor operating on the principle of continuous hydroformylation of butene-2 by passing through once. The reactor consists of a thick-walled bottle with a capacity of 90 ml immersed in an oil bath with a glass window for observation. After purging the system with nitrogen, approximately 20 ml of a freshly prepared solution of the rhodium catalyst precursor is loaded into the reactor using a syringe. The precursor solution contains approximately 125 ppm of rhodium, administered as rhodium dicarboxy-acetylacetonate, about 7.0 wt% of bis-phosphite ligand (approximately 50 mol of ligand per mole of rd), and yes, as a solvent trimer. The reactor is closed, the system is purged with nitrogen again and the oil bath is heated with a burner to the desired reaction temperature of the hydroformylation. The hydroformylation reaction is carried out at a total gas pressure of about 11.2 atm5, where the partial pressures of hydrogen, carbon monoxide and butene-2 correspond to the values given in table. 9, and the rest is nitrogen and aldehyde product. Flows of feed gases (carbon monoxide, hydrogen and butene-2) are controlled individually by flow meters and the feed gases are dispersed in the solution of the precursor through glass filtering filters, barbotero. Reaction temperatures are given in Table. 9. The flow of unreacted feed gas introduces
20
25
thirty
35
40
H
one
The resulting C5 aldehydes and exhaust gases are analyzed for approximately 15 days of continuous operation. In tab. 9 shows the approximate daily values of the reaction rates, expressed in mol / l / h, based on the aldehydes C5 obtained, and the molar ratios of the linear n-valanaldehyde to the branched 2-methyl aldehyde in the product.
Example 12. Butene-2 (molar1 ratio of cis- and trans-isomers of butene-2 is approximately 1: I) —the hydrophore is §5 milled as in Example 9 using the bis-phosphite ligane of the following formula:
UFO (SNZ) s S (SNZDO

SSSNz

0
five
0
five
0
five
0
five
0
five
The hydroformylation is carried out in a glass reactor by continuously passing one butene-2. The reactor is made up of a thick sklyan
with a capacity of 90 cp, foot, so-called ° pus in an oil bath with a glass window for attachments. After purging the system {with nitrogen, approximately 20 ml of a freshly prepared solution of the rhodium catalyst precursor is loaded into the reactor using a syringe. The precursor solution contains approximately 223 ppm of rhodium, administered as dicarbochyl acetylacetonate, about 1.8% by weight of the bisphosphite ligand (about 8.3 mol of ligand per mole of rhodium) and hexanol as a solvent. The reactor is closed, the system is purged with nitrogen again, and the oil bath is heated with a burner to the desired reaction temperature of the hydroforkylation agent.
The hydroformylation reaction is carried out at a total gas pressure of about 11.2 atm with partial pressures. hydrogen, carbon monoxide and butene-2s listed in Table 10; the remainder is nitrogen and the aldehyde product. The feed gas streams (carbon monoxide, hydrogen and butene 2) are individually controlled using flow meters and the feed gases are dispersed in the precursor solution through glass sparging filters. The reaction temperature is listed in Table 10. The unreacted feed gas stream carries off the resulting aldehyde C5 and outgoing gas is analyzed for approximately 5.5 days of continuous operation. The approximate average daily values of the reaction rate, expressed in mol / l / h based on C5 aldehyde products; and the molar ratio of linear n-valanaldehyde to branched 2-methyl aldehyde in the product is presented in table 10.
Example
formula ligand
13, Bis-phosphitic (garden.
HSCO
, 2-dipole as follows.
About 179.2 g (0, S mol 2, hydroxy-3-3-di-tert-butyl-5.5f-dimetho si-1,1-diphenyldiol is added to about 1600 ml of toluene. Then, azeotropically the amount is removed. toluene, which is sufficient to remove residual traces of moisture.Then the di-toluene solution is allowed to cool to approximately 80 ° C and about 168.7 g (1.67 mol) of triethylamine are added.
Approximately 68.7 g (0.5 mol of phosphorus trichloride in approximately 200 ml of toluene is added, followed by a solution of diol toluene triethylamine added dropwise at -10 ° C for approximately 100 minutes. The reaction solution is kept at This temperature is approximately 30 minutes and allowed to warm to room temperature over 2 hours. The reaction medium is then filtered, the solid precipitate of triethylamine hydrochloride is removed and washed with two 200 ml portions of toluene. The filtrate and washings are combined, concentrated and approximately tionary 717.5 g of a solution fosforhlo- riditnogo intermediate compound of the following formula:
(CH j
SNZO /
P-C1
ch3- o-o ctCHib
About 170.3 g of additional 2.2-dioxy-3,3-di-tert-butyl-5, 51-dimethoxy-1, 1-diphenyldiol, and then about 48.1 g of triethylamine are added to approximately 800 ml of toluene. 717.5 g of the indicated toluene solution of phosphorus chloride is added dropwise at room temperature for approximately 45 minutes, the temperature is raised to approximately
0
five
0
five
80 ° C for 105 minutes, then for 2 hours the temperature is raised to about 95 ° C and the mixture is allowed to cool to room temperature. About 600 ml of distilled water was added to dissolve the solid precipitate of triethylamine hydrochloride, after which it was allowed to stand and separate into two layers. The aqueous layer was extracted with two 250 ml portions of toluene. The organic layer and extracts were combined, dried over anhydrous magnesium sulphate for 1 h, filtered and concentrated under vacuum to give a residue. Thereafter, the residue is recrystallized from acetonitrile, and approximately 242} 5 g (yield about 65.4% of theoretical) of the dorganophosphite intermediate compound of the following formula is isolated:
СНЗО CVhO
(CH3) s
C (CH3-) 3
thirty
Approximately 242.5 g of the indicated recrystallized diorganophosphite intermediate was added to 1 l of toluene, and then about 31.4 g of triethylamine. After that, drop by drop for about
0 5 minutes at room temperature, about 42.7 g of phosphorus trichloride are added, and then boiling under reflux for approximately 3 hours and 45 minutes. The reaction solution is cooled to approximately 68 ° C and about 1 g of triethylamine and then about 2 t, 3 g of phosphorus trichloride are added. The reaction mixture is heated under reflux for approximately 16 hours. The suspension is then cooled to 20 ° C, filtered and the solid precipitate of triethylamine hydrochloride is removed, which is washed with two 200 ml portions of toluene. The filtrate and washings are combined, concentrated under vacuum, and approximately 516.2 g of a toluene solution of the following phosphorus dichloridite intermediate are obtained:
Ligand 3.
Approximately 500 ml of toluene. About 79.9 g of para-chlorofenol and then about 62.9 g of triethyl amine are added. Then, 516.2 g of the indicated toluene phosphorus dichloride solution is added dropwise at room temperature for about 115 minutes. The reaction solution is allowed to stir at room temperature for an additional 135 minutes. Then, about 600 ml of distilled water was added to dissolve the solid precipitate of triethylamine hydrochloride and the solution was allowed to settle until it was divided into two layers. The aqueous layer is then extracted with two 250 ml portions of toluene. The organic layer and extracts are combined, dried over magnesium sulfate, filtered, and concentrated under vacuum to obtain a residue. The latter is recrystallized from acetonitrile and approximately 200 g (about 62.5% of theoretical yield) of the desired bis-phosphite ligand of the above formula9 referred to as ligand 1 is isolated:
1sn, ъ СНзД
Sn С (СНз sn10- о о х х o / ovci
sn3 o h
/

WITH(
Similarly, bis7 phosphite ligands (ligands 2–8) are prepared with 45 using suitable diphenolic and mono-salt compounds of appropriate structure,
Ligand 2
CH30 OCH3 (SNZ) 3 ±
9 (sn3) (ciss) s
CH30- About Och
.OSNg
axes
CHJO MAIN
Ш30
CH30

with
(CH3) 3
Ligand 4.
CH30
(ss A
С (СН30-Н) -0CH-iO-W-0-X
c (rnz
Ligand 5.
OCHj
-С (СН3) 3 / СН§ С9Н19
ocho
H3CO
Ssnz) 3A
J5 Shnz) 3s- (oi
-about
t
sn3- (d m
SNZO-CHYO-S (CH3
Ligand 6.
-ABOUT
(SNIZ SSNz

(9, n & rnc (CH3bc-t0
(sn3) 3c- (o) -c
(СНз) 3С-Ю) -0Х
LU.
C (W313 Ligand 7.
Ј Ј
Jj (CH3) jO (CH313C-0-0X6
/ h / p
(SNZ C-HOW-O
(CHjh Ligand 8.
0KSNz
50
(OTD and
55
SN-CHO CH30
The structures of the bis-phosphite ligands described are confirmed using nuclear phosphorus-31 nuclear magnetic resonance spectroscopy (P-311 NMR) and accelerated-atom bombardment mass spectroscopy (MSBRA). Bis-phosphorus ligands can be identified by their characteristic R-31 NMR spectrum (i.e., pairs of doublets, showing the exchange constant of phosphorus-phosphorus (IP1-P2 (Hz)), and by IASB, showing the mass, corresponding to the mass of the molecular ion of a given bisphosphite, as is seen, for example, from
presented in Table. khih data.
11 analytically Example 14. A bisphosphite ligand rhodium complex (said ligand is ligand 3} obtained in Example 13) is prepared as follows.
To a solution of 0.5 g (0.5 mmol) of the indicated ligand in 10 ml of dichloromethane was added 0.1 g (0.25 mmol) of chlorofibrobysylrodium dimer RhCl (CO) 1Ji. The mixture was stirred at room temperature for 4.5 hours. to complete the reaction, as indicated by the cessation of carbon monoxide release. Then, the reaction solution is concentrated under vacuum to obtain a residue, which is recrystallized from hexane, to obtain 0.14 g of a crystalline solid compound, which according to X-ray diffraction analysis, is uniquely identified as the cis-chelate chlorocarbonyl rhodium complex of the indicated ligand, having the following formula:
CH30 (CH3
5 "hell (oU-o- P
, /
(C / -0
C (CHU
The P-31 NMR spectrum of this complex product in solution also corresponds to the cis-chelate rhodium complex.
The said rhodium-bis-phosphite complex (in Table 12, designated as complex A) is used to hydroformy propylene analogously to example 2 and it is established that it possesses a very high hydroforming ratio.
five
general activity under the conditions described in Table. 12, despite the presence of rhodium-bound chloride. This rhodium-bis-phosphite complex catalyst is also compared with a rhodium bisphosphite ligand complex catalyst containing the same ligand, but not containing chloride and
Q obtained not from ЈRhCl (CO) 2 s but from dicarbonylacetylacetonate rhodi. In tab. 12, this rhodium ligand complex, free of chloride, is designated as complex B. In the table. 12 also listed
5, the rate of the hydroformylation reaction, expressed in mol / l / h in the p-scale, on the resulting oil aldehyde, as well as the molar ratio of the linear n-oil aldehyde to the branched iso-butyric aldehyde in the resulting product.
Conditions; 250 ppin rode; 7 atm H,: CO: propylene (molar ratio 1: 1: 1).
Although the rhodium catalyst of complex A exhibits good activity, however, its rhodium-bound chloride has a negative effect on achieving a high ratio of linear aldehyde to branched product, therefore its use should be avoided when a high ratio of normal aldehyde to isomeric is required. branched aldehyde.
As can be seen from the above examples, the proposed method allows to obtain a hydroformylation product with a ratio of normal and isothermaldehydes to 93, which significantly increases the selectivity of the process for n-aldehyde. For comparison: the prototype provides for obtaining the target product with a ratio of normal and isothermaldehydes, usually not exceeding the value of 15-20.

权利要求:
Claims (1)
[1]
Claim 0
The method of producing aldehydes, by hydroforming the olefins with carbon monoxide and hydrogen at a temperature of 60-120 ° C, dab pressure of 3.5-11.2 atm, partial pressure of hydrogen 1.4-6.69 atm, partial pressure of carbon monoxide 0.7- 8.4 atm in the presence of rhodium-containing0
five
0
five
a common catalytic system, including rhodium dicarbonylacetylacetonate, taken in the amount of 112-400 ppm per rhodium and phosphorus-containing ligand with a molar ratio of ligand and rhodium equal to 4-58.8: 1, it is In order to increase the selectivity of the process for n-aldehyde, the bis-phosphite ligand of the general formula is used as the phosphorus-containing ligand.
Ag-0x
P-O-W-O-P
, Oz
X
Qz
Note a b c d
e
250 ppm rhodium, 2 wt.% Bis-phosphite ligand;
70 ° CJ 7 atm. CO2: He (molar ratio 1: 2);
2.45 atm of butene-1 (2.5 ml of butene-1);
330 ppm give birth; 2 wt.% Bis-phosphite ligand;
70 ° C, 3.5 atm SOZN. (molar ratio 1: 4);
2.5 ml of butene-1;
toluene;
valeric aldehyde trimer;
hexanol.
Where
c (snen
or (III) 3C- (O
W-%
OR
15
where Rj-R is together or separately hydrogen or OCHE, or tert-butyl,
- HN. CFiH
$ 6% P-NONIL
n-ClCgttg-, o-tolyl,
С6Ч5,
C9H19
Table 1
N o. A b c d
2.41 4.69 2.5
table 2
330 ppm rodi; 7.5 mol bis-phosphite
ligand per mole of rhode; 85 ° C, 5.25 atm
CO: H2: propylene (molar ratio 1: 1: 1);
250 ppm rhodium, 4 mol bis-phosphite
ligand per mole of rhodium, 70 ° C; 6.3 atm
CO: Ng: propylene (molar ratio 1: 1: 1) i
toluene;
valeric aldehyde trimer.
Table 3
0
3.05
1.5
3.5
0.36
2.1
0.2
1.2
0.15
68
16 66
19 93 17 80 14
Table 4
Table 5
25
The isomeric ratio in the stream was not measured.
A change in value corresponds to a daily change in concentration
solution in a liquid reactor.
1537133
26 Table b
27
1537133
A change in the values corresponds to a daily change in the concentration of the solution in the liquid reactor.
28 Table
Table 10
Table 1G

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同族专利:

公开号 | 公开日

PL261285A1|1987-10-05|

DK423086D0|1986-09-04|

SK642986A3|1996-09-04|

AU598749B2|1990-07-05|

HU204747B|1992-02-28|

JPH06166694A|1994-06-14|

EP0213639B1|1991-06-26|

MX3655A|1993-12-01|

FI863569A|1987-03-06|

KR870003128A|1987-04-15|

YU45798B|1992-07-20|

PL147093B1|1989-04-29|

NO172494B|1993-04-19|

CN86106770A|1987-05-13|

FI863569A0|1986-09-04|

CZ843488A3|1998-07-15|

CA1271773A|1990-07-17|

JPS62116587A|1987-05-28|

CZ284301B6|1998-10-14|

CZ284335B6|1998-10-14|

IN168017B|1991-01-19|

CN1019104B|1992-11-18|

SK278287B6|1996-08-07|

AR242218A1|1993-03-31|

AT64739T|1991-07-15|

DE3679945D1|1991-08-01|

FI85863C|1992-06-10|

NO863547L|1987-03-06|

JPH07108910B2|1995-11-22|

NO172494C|1993-07-28|

YU154986A|1988-06-30|

HUT47515A|1989-03-28|

NO863547D0|1986-09-04|

JPH0580264B2|1993-11-08|

BR8604262A|1987-05-05|

ZA866729B|1987-04-29|

DK423086A|1987-03-06|

KR930001327B1|1993-02-26|

EP0213639A3|1988-01-13|

ES2001654A6|1988-06-01|

AU6237286A|1987-03-12|

SK278296B6|1996-09-04|

EP0213639A2|1987-03-11|

CZ642986A3|1998-07-15|

FI85863B|1992-02-28|

US4748261A|1988-05-31|

SK843488A3|1996-08-07|

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法律状态:
2007-09-20| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20040905 |

优先权:

申请号 | 申请日 | 专利标题

US06/772,891|US4748261A|1985-09-05|1985-09-05|Bis-phosphite compounds|

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