CN1045953C - Process of preparation for normal isomeric aldehyde with low-concentration olefinic compound - Google Patents
Process of preparation for normal isomeric aldehyde with low-concentration olefinic compound Download PDFInfo
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- CN1045953C CN1045953C CN94114289A CN94114289A CN1045953C CN 1045953 C CN1045953 C CN 1045953C CN 94114289 A CN94114289 A CN 94114289A CN 94114289 A CN94114289 A CN 94114289A CN 1045953 C CN1045953 C CN 1045953C
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Abstract
The present invention provides a process for preparing normal isomeric aldehyde with low concentration olefin in a carbonyl synthesis mode. In the present invention, 5 to 40% of low-concentration olefin with 2 to 6 carbon atoms is used as raw materials, metal organic complexes are loaded on a porous carrier in a liquid phase form, and are prepared into catalysts under the existence of ligand, ao that aldehyde is generated through hydroformylation reaction under a milder condition. The present invention has the advantages of selectivity which is greater than 85% to 98%, high stability, life time which is greater than 2000 hours and olefin conversion rate which is greater than 85%, and has favorable industrialized prospects.
Description
The present invention relates to a kind of low-concentration olefinic in the presence of hydrogen and carbon monoxide, prepare the method for positive isomery aldehyde through carbongl group synthesis reaction.
Since the seventies, a large amount of research was once carried out in above-mentioned reaction abroad, particularly Dutch J.F.Scholten leader's research group has delivered many articles and has applied for patent (US4193942) in this field.But all patent documentations all do not report with low-concentration olefinic and react with raw material, all with pure alkene as research object.And in industrial production, have a large amount of low-concentration olefinics, handle as waste gas or fuel gas usually.The dry gas that generates of refinery catalytic cracking for example wherein contains the ethene of 10-20%, and the hydrogen of 26-30% acts as a fuel usually and burns.Another shortcoming of foreign study work is that its catalyst system therefor is long inductive phase, and stability is low, and activity is not high, and it is very difficult to carry out suitability for industrialized production.
The objective of the invention is to overcome raw material olefin purity requirement height in the prior art, the catalyst inducement phase is long, the shortcoming of poor stability and provide a kind of lower concentration hydrocarbon hydrocarbon to prepare the method for positive isomery aldehyde through oxo process.
The present invention realizes by following measure:
A kind of low-concentration olefinic prepares the method for positive isomery aldehyde through carbongl group synthesis reaction in the presence of hydrogen and carbon monoxide, comprising:
1. select the 2-6 carbon atom alkene of 5-40% for use;
2. use with porousness solid phase carrier Al
2O
3, SiO
2, molecular sieve, organic polymer, active ingredient
Be organometallic complex Co
2(CO)
8, RhHCl (PPh
3)
3, RhHCO (PPH
3)
3, Rh
6(CO)
16,
RhCl
3, RhAc catalyzer;
3. alkene: oxygen: carbon monoxide is 1: 1: 1-1: 2: 3
4. operational condition is under 50-150 ℃ of pressure 0.1-4.0MPa, air speed (GHSV) 300-30000/h
Generate aldehyde.
The support of the catalyst shape that the present invention selects for use is not limit, and can be spherical, can be bar-shaped yet, or random shape, or colloidal state.
The liquid phase loading 0.01-1.10cm of carrier
3/ cm
3Volume does not wait.For making catalyzer reach best effect, preferably make the filling ratio in its hole reach 0.3-0.8.
Preparation of Catalyst can adopt several different methods, and a kind of is with carrier organometallic complex solution impregnation, and another kind is to adopt the inertia secondary solvent, makes active ingredient and this solvent form solution, impregnated on the carrier, then this solvent is removed.This solvent can be benzene,toluene,xylene, formaldehyde, ethanol etc.
The present invention can be converted into aldehyde with the dilute alkene of 2-6 carbon atom.Reaction preference＞95%, olefin conversion＞90%, stability＞2000 hours.
In sum, the present invention has following advantage:
One, low to the unstripped gas requirement, as long as wherein there is 5% above alkene to react.
Two, Preparation of Catalyst is simple.
Three, catalyst performance stabilised, catalytic activity height, reaction preference height.
Four, reaction conditions gentleness, the temperature range broad, reaction pressure is lower.
Implementation of the present invention and embodiment:
Embodiment 1: the dry gas that adopts refinery to provide, and this dry gas is composed as follows: ethene 12.60%, hydrogen; 30.00%, nitrogen: 14.50%, propylene 10.29%, ethane: 10.44%, methane: 10.39%, also contain Determination of Trace Sulfur and oxygen and butane, butylene etc. in addition.With Al
2O
3Make carrier, with HRhCO (PPh
3)
3Prepare catalyzer as active ingredient, experiment is carried out on miniature fixed bed high pressure reaction assembly.Reactor inside diameter 0.006M, catalytic bed height 0.035M, catalyst levels 1ml, catalyst grain size 20-60 order, dry gas pressure 0.6Mpa is pressurized to 3.0-4.0Mpa, is equipped with CO and H again
2Make alkene/CO/H
2Be 1/1/1 or 1/1/2, reaction result sees Table 1.
Table 1
| Propionic aldehyde selectivity % | Conversion of ethylene % | Product liquid distribution % | ||
| Propionic aldehyde | Butyraldehyde-n | N-propyl alcohol | ||
| 98 | 91.2 | 95.0 | 6.9 | 1.7 |
Reaction conditions: T=103.0 ℃, GHSV=1800/h alkene/CO/H
2=1/1/1.5
Embodiment 2: unstripped gas is with example 1, and support of the catalyst adopts porous polymer beads (GDX), reaction pressure: P=1.5Mpa, T=130 ℃, GHSV=1150/h, alkene/CO/H
2=1/1/1.5 reaction result sees Table 2.
Table 2
Embodiment 3: catalyzer repeatability is one of important indicator of heterogeneous catalyst, and the SLPC for preparing has been investigated its repeatability from different aspects, the results are shown in Table 3.
| Propionic aldehyde selectivity % | Conversion of ethylene % | Product liquid distribution % | ||
| Propionic aldehyde | Butyraldehyde-n | N-propyl alcohol | ||
| 97 | 88.9 | 83.0 | 10.8 | 4.0 |
Table 3. different batches SLPC/GDX specific activity
Reaction conditions: T=90.0 ℃, P=1.5Mpa, GHSV=1200/h embodiment 4: adopt different batches Al
2O
3Make carrier, reaction result sees Table 4.
| Numbering | Conversion of ethylene % | Propionic aldehyde selectivity % |
| G-01 G-02 G-03 | 90.0 98.5 91.3 | 95.4 96.0 94.7 |
Table 4
| Numbering | Conversion of ethylene % | Propionic aldehyde selectivity % |
| A-01 A-02 A-03 A-04 | 87.6 88.0 86.8 87.5 | 96.0 95.5 96.2 95.0 |
T=110 ℃, P=1.5Mpa, GHSV=1500/h embodiment 5: adopt the reaction gas of example 1, with Rh
6(CO)
16As the catalyst activity component, with SiO
2Support of the catalyst, temperature of reaction T=100 ℃, reaction pressure P=0.5Mpa, GHSV=1200/h, alkene/CO/H
2=1/1/1, reaction result sees Table 5.
Table 5
Embodiment 6: the gas reaction unstripped gas that contains 10% propylene that utilizes the F-T reaction to generate, and with RhCl
3Make active ingredient, SiO
2Make support of the catalyst, with PPh
3Make as solvent that liquid phase is catalyst-loaded reacts, reaction conditions is as follows: 70 ℃ of temperature, pressure: 1.5Mpa, GHSV=1300/h, alkene/CO/H
2=1/1/1.5 reaction result sees Table 6.
| Propionic aldehyde selectivity % | Conversion of ethylene % | Product liquid distribution % | ||
| Propionic aldehyde | Butyraldehyde-n | N-propyl alcohol | ||
| 94.6 | 90.4 | 94.1 | 7.2 | 1.5 |
Table 6
Embodiment 7: the 5-10% ethylene gas that adopts oxidative coupling of methane to generate is made raw material, makes active ingredient with RhAc, Al
2O
3Make support of the catalyst, HAc makes solid-phase catalyst as solvent, under the following conditions reaction: 120 ℃ of temperature, pressure: 1.5Mpa, GHSV=1000h, alkene/H
2/ CO=1/1/1, reaction result sees Table 7.
| Propionic aldehyde selectivity % | Conversion of ethylene % | Product liquid distribution % | ||
| Propionic aldehyde | Butyraldehyde-n | N-propyl alcohol | ||
| 92.8 | 89.6 | 91.3 | 7.8 | 2.1 |
Table 7
Embodiment 8: adopt example 1 reaction gas and catalyzer, investigate catalyst life under the following conditions, wherein temperature of reaction: 80 ℃, and pressure: 1.0Mpa, GHSV=1200/h, alkene/H
2/ CO=1/1/1, reaction result sees Table 8.
| Propionic aldehyde selectivity % | Conversion of ethylene % | Product liquid distribution % | ||
| Propionic aldehyde | Butyraldehyde-n | N-propyl alcohol | ||
| 95.1 | 93.2 | 91.8 | 5.2 | 2.8 |
Table 8
Embodiment 9: adopt example 1 reaction gas and example 2 catalyzer, investigate catalyst life under the following conditions, temperature of reaction: T=110 ℃, and GHSV=1300/h, alkene/H
2/ CO=1/1/1, reaction result sees Table 9.
| Propionic aldehyde selectivity % | Conversion of ethylene % | Life-span (hour) |
| ＞94 | ＞90 | 2128 |
Table 9
Embodiment 10: adopt example 1 reaction gas to make raw material, with Co
2(CO)
8Make active ingredient, make carrier, PPH with molecular sieve
3Make as solvent and to support liquid-phase catalyst, under the following conditions it has been done investigation, result such as table 10,80 ℃ of temperature of reaction, pressure 4Mpa, GHSV=800/h, alkene/CO/H
2=1/1/1
| Propionic aldehyde selectivity % | Conversion of ethylene % | Life-span (hour) |
| ＞93 | ＞91 | 2481 |
Table 10
| Propionic aldehyde selectivity % | Conversion of ethylene % | Life-span (hour) |
| ＞87 | ＞85 | 1370 |
Claims (3)
1. a low-concentration olefinic prepares positive isomery aldehyde method through carbongl group synthesis reaction in the presence of hydrogen and carbon monoxide, comprising:
(1) select the 2-6 carbon atom alkene of 5-40% for use,
(2) use with porousness solid carrier Al
2O
3, SiO
2, molecular sieve, organic polymer, work
The property component is organometallic complex Co
2(CO)
8, RhHCl (pph
3)
3, RhHCO (PPH
3) Rh (CO)
16, RhCL
3, RhAc,
(3) alkene: hydrogen: carbonoxide is 1: 1: 1-1: 2: 3,
(4) operational condition is temperature 50-150 ℃, pressure 0.1-4.0Mpa, and air speed is 300-3000/h
Under generate aldehyde.
2. as the said method of claim 1, it is characterized in that support of the catalyst is shaped as spherical, bar-shaped or random shape or colloidal state, the liquid phase loading 0.01-1.10cm of carrier
3/ cm
3
3. as the said method of claim 2, the filling ratio that it is characterized in that the support of the catalyst hole is 0.3-0 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94114289A CN1045953C (en) | 1994-12-28 | 1994-12-28 | Process of preparation for normal isomeric aldehyde with low-concentration olefinic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94114289A CN1045953C (en) | 1994-12-28 | 1994-12-28 | Process of preparation for normal isomeric aldehyde with low-concentration olefinic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1125712A CN1125712A (en) | 1996-07-03 |
| CN1045953C true CN1045953C (en) | 1999-10-27 |
Family
ID=5037180
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94114289A Expired - Fee Related CN1045953C (en) | 1994-12-28 | 1994-12-28 | Process of preparation for normal isomeric aldehyde with low-concentration olefinic compound |
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|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112830870A (en) * | 2019-11-25 | 2021-05-25 | 南京延长反应技术研究院有限公司 | Enhanced reaction system and process for preparing isomeric aldehyde by olefin carbonylation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0245893A2 (en) * | 1986-05-13 | 1987-11-19 | Shell Internationale Researchmaatschappij B.V. | Catalyst compositions |
| EP0560455A1 (en) * | 1992-03-11 | 1993-09-15 | ENICHEM S.p.A. | Catalytic system and process for copolymerizing carbon monoxide with one or more olefins |
| EP0589463A2 (en) * | 1992-09-25 | 1994-03-30 | Mitsubishi Chemical Corporation | A method of controlling a hydroformylation reaction |
-
1994
- 1994-12-28 CN CN94114289A patent/CN1045953C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0245893A2 (en) * | 1986-05-13 | 1987-11-19 | Shell Internationale Researchmaatschappij B.V. | Catalyst compositions |
| EP0560455A1 (en) * | 1992-03-11 | 1993-09-15 | ENICHEM S.p.A. | Catalytic system and process for copolymerizing carbon monoxide with one or more olefins |
| EP0589463A2 (en) * | 1992-09-25 | 1994-03-30 | Mitsubishi Chemical Corporation | A method of controlling a hydroformylation reaction |
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| Publication number | Publication date |
|---|---|
| CN1125712A (en) | 1996-07-03 |
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