CN1422695A - Catalyst for preparing various of organic aldehyde by alefin hydro-formylation and preparation method thereof - Google Patents
Catalyst for preparing various of organic aldehyde by alefin hydro-formylation and preparation method thereof Download PDFInfo
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Abstract
The catalyst for preparing various organic aldehydes by utilizing olefine hydrogen formylation mainly is formed from active componnet, adjuvant, carrier and organic homogeneous catalyst ligand, its active component is Rh, Pt, Ru or Pd, the adjuvant is from metal elements of periodic family VB or IVB or VIB, such as V, Ti, Zr and Mn, etc, and its carrier can select and use silicon dioxide, MCM-41, active carbon or Al2O3, etc. and the organic homogeneous catalyst ligand can select and use triphenylphosphine, sodium triphenylphosphine trisulfonate, triphenylphosphine oxide, tricyclohexaalkyl phosphine or triphenol phosphine. Their contents are: active component is 0.01-5.0%, adjuvant element is 0.01-10.0%, organic homogeneous catalyst ligand is 0.01-30.0%, and the addition of the adjuvant can effectively improve reaction and stability properties of catalyst.
Description
Technical field
The invention provides a kind of catalyzer and this Preparation of catalysts method of producing all kinds of organic aldehydes by olefin hydroformylation.
Background technology
From Germany scientist O.Roelen in 1938 since (1897-1993) find olefin hydroformylation (claiming OXO-Synthesis again); its research and development are contained for a long time always and are not waned, and it becomes most important organic chemical industry's production technique when the world with the output of ten thousand tons of annual 700-800.Its product spreads all over the aldehyde and the alcohol of various different carbon numbers, and is wherein topmost except that the synthetic fourth of being set out by propylene, octanol (2-Ethylhexyl Alcohol), is the C of raw material when calculating with the higher olefins
8～11Plasticizer alcohol and C
12～18Surfactant alcohols.The consumption of nineteen ninety-five whole world plasticizer alcohol (not containing 2-Ethylhexyl Alcohol) and surfactant alcohols reaches 1,500,000 tons and 1,200,000 tons respectively.
In the hydroformylation catalyst of industrial application up to now, rhodium catalyst is with its catalytic activity height, characteristics such as selectivity is good, reaction conditions is gentle, energy consumption is lower, facility investment is less and become the first-selection of hydroformylation of propene.At present, the technology of hydroformylation of propene system fourth, octanol, use the 3rd generation rhodium/phosphine catalyst more than 90%.Yet in the production of the high carbon number alcohol of using hydroformylation of higher olefins system, 90% product still adopts cobalt-base catalyst.This is the boiling point height because of high carbon number alcohol, and during at high temperature by flash distillation and catalyst separating, rhodium catalyst will be decomposed.In addition, rhodium catalyst is being that activity in the synthetic plasticizer alcohol process of raw material is good inadequately with branched-chain alkene (dibutene or tripropylene), and when setting out synthetic fatty alcohol with normal olefine, the positive structure rate of product is relatively poor.
In recent years, the work of rhodium catalyst hydroformylation is mainly concentrated both ways: the one, by improving part to obtain better, the active higher phosphine/rhodium catalyst of stability; The 2nd, the process for separating and recovering of innovation catalyzer.Japan Mitsubishi Kasei company has successfully developed the isononyl alcohol synthetic technology, and it is catalyzer that this technology is used triphenylphosphine oxidation thing (TPPO)/rhodium instead.Ruhrchemie company succeeded in developing hydroformylation of propene system butyraldehyde-n a new generation Catalytic processes in 1984.It is that title complex with sodium trisulfonate (TPPTS)/rhodium between the water-soluble phosphine ligand triphenylphosphine is a catalyzer, finishes in water/organic two-phase system, and reaction can separate catalyzer and product by simply being separated after finishing.
The key problem of even phase complex catalysis is the separation of metal catalyst and recycles.Can be divided into two big classes on the even phase catalysis heterogenize methodological principle that generally adopts for head it off, a class is with the immobilized even phase catalysis of catalyzer stationary on polymer or inorganic carrier; The another kind of water-soluble phosphine ligand that then adopts, will spare phase catalyst dynamically " load " at water/organic biphasic catalysis of realizing with the immiscible water of product.Immobilized even phase catalyst is through further investigation decades, and therefore the problem that still unresolved metal comes off and runs off does not have industrialized report so far.Form sharp contrast with it, the biphasic catalysis system is keeping even phase catalytic activity height, in the time of characteristics such as the good and reaction conditions gentleness of selectivity, possess heterogeneous catalyst product and catalyzer again to be easy to isolating superiority, beginning embodies extensive applicability in catalyzed reaction.
U.S.P.4248802 has reported that the water/organic phase catalyst system of rhodium/sulfonated triphenylphosphine is used for the process of the hydroformylation reaction generation aldehyde of alkene.U.S.P.5354908 is the patent of U.S. EXXON company application, and this provides the method that volatile cobalt-based complex compound is transformed into a kind of nonvolatile cobalt-base catalyst, and this catalyzer can be used in the hydroformylation reaction of alkene.
U.S.P.5585524 has invented a kind of cobalt-based complex compound catalyst system that olefin hydroformylation is produced aldehyde compound that is used for; this catalyst system adopts the two-phase system of polar organic phase/organic phase, and the cobalt-based complex compound is separated from organic phase mutually by being dissolved in polar organic like this.This catalyst system is applied to the hydroformylation reaction of ethene, and its reaction pressure and temperature of reaction all are lower than the cobalt carbonyl catalyst of single organic phase.And the cobalt-based complex compound catalyst has separated simply with organic solvent and product.
U.S.P.5731472 is the patent by the union carbide corporation application, this patented invention a kind of metal-organic many phosphite ligands complex compound catalyst, this catalyzer has advantages of higher stability.Recently, the patent U.S.P.6175043 of Dupont company invention has described a kind of technological process that is used to prepare linear chain aldehyde, and the used catalyzer of this process is made up of VIII family metal and organic phosphite part, and wherein ligand structure is as follows: P (OR)
2-OR ' O-P (OR)
2Or P (OR)
3, R, R ' are at least 9 to 40 fatty group for carbon number.
U.S.P.6184413 is the patent of California Institute of Technology's application, has reported a kind of load phase catalyst, and the load of this catalyzer is strong polarity mutually, as ethylene glycol or glycerol; Its metal center is sulfonated 2,2 '-two diphenylphosphines-1 of chirality, 1 ' two naphthalide complex compounds, and this complex compound dissolves in the load mutually, and this class catalyst system can be used for having optically active asymmetric synthesis.
As mentioned above, how immobilized the thinking that solves at present the separation of even phase catalytic metal catalyzer and recycle the problem way all be or be separated from even phase catalyst, therefore, above-mentioned these catalyst systems still fail to solve fully the problem that catalyzer separates and recycles with product.
Summary of the invention
In order to address the above problem, the purpose of this invention is to provide a kind of novel catalyst system of producing all kinds of organic aldehydes by the alkene hydroformylation.
How modification makes it become the high reactivity with even phase catalyst to inventors of the present invention from heterogeneous catalyst to nobody's consideration so far, and highly selective and reaction conditions have carried out research repeatedly.Proposed to form catalyst system with the transition metal ion in the alternative homogeneous complex catalyzer of metallic particles in the metal supported catalyst (heterogeneous catalyst) (forming) by tens or up to a hundred atoms metals, that is to say, load or absorption or the organic ligand that absorbs even phase catalyst become new catalyst system again in metal supported catalyst, promptly, adopt the even method of changing mutually of heterogeneous catalyst, and then finish the present invention.
Specifically, catalyst system provided by the invention is made up of main active metal component, auxiliary agent, carrier and organic ligand four parts.Main active ingredient is the VIII metal, mainly is metal Ru, rhodium, palladium or platinum, and wherein the activity of rhodium is the highest; Auxiliary agent is that as V, Nb, Ta, Ti, Zr, Hf, Mn, Tc or Re, wherein V, Ti, Zr or Mn are better from VB or IVB or VIA family metallic element, and only be V; Carrier is selected silicon-dioxide, MCM-41, gac or aluminium sesquioxide etc., the optimum silicon-dioxide of selecting for use for use; Organic even phase catalyst part is selected triphenylphosphine, sulfonated triphenylphosphine, triphenylphosphine oxide, three cyclohexyl phosphines or three phenolic group phosphines etc., optimum triphenylphosphine and the sulfonated triphenylphosphine selected for use for use.In addition, active ingredient accounts for 0.01-5.0% in total catalyst weight.Auxiliary element accounts for 0.01-10.0% in total catalyst weight, and the gross weight of organic even phase catalyst part in catalyzer is 0.01-30.0%.Active ingredient accounts for 0.01-1.0% in the total catalyst weight and be preferably in, and auxiliary agent is 0.1-5.0%, organic even phase catalyst ligand 1 .0-20%.
In addition, in above-mentioned catalyzer, the specific surface area of carrier is at 150m
2/ g-400m
2/ g, pore volume 0.5-2.0cm
3/ g, pore size distribution are 4-1000 .
Above-mentioned Preparation of catalysts of the present invention comprises the preparation of heterogeneous catalyst and the organic even phase catalyst part of made catalyst soakage is obtained the purpose catalyzer.The preparation method of heterogeneous catalyst is simple and reliable, with the metal of active ingredient and the solubility salt of all auxiliary elements, for example the aqueous solution of nitrate, carbonate or carbonyl compound adopts conventional pickling process, be immersed on the above-mentioned carrier, drying is used hydrogen reducing, and reduction temperature is 100-600 ℃, pressure is normal pressure, and the recovery time is 1-30 hour.Then, the phosphine part of sparing phase catalyst is dissolved in organic solvent or the water, adopts conventional pickling process, be immersed on the above-mentioned heterogeneous catalyst, the drying of finding time removes solvent.Promptly finish the even preparation of changing mutually of heterogeneous catalyst.
In above-mentioned preparation method, when the phosphine part is triphenylphosphine, triphenylphosphine oxide, three cyclohexyl phosphines or during at the phenolic group phosphine, dissolve with organic solvent, used organic solvent can use pentane, hexane or hexanaphthene etc.And the phosphine part is when being the triphenylphosphine sodium trisulfonate, and water dissolves.
Use catalyst system of the present invention to carry out the hydroformylation reaction of alkene, can in slurry attitude bed process, carry out.Its typical operational condition is: slurry attitude bed reaction conditions, and 80-150 ℃, 0.5-10.0MPa, 600-1200r/min can adopt gap reaction or continuous flow reaction, and the granularity of catalyzer is the 180-250 order.Catalyzer reaction evaluating in slurry attitude bed shows that the heterogeneous catalyst of this patent invention is even changes catalyzer mutually, have the very selectivity (near 100%) of high conversion (near 100%) and aldehyde, but catalyst separating is simple and the recirculation use.Below further be described by example:
Embodiment example 1.
Take by weighing 10 gram silica gel (Haiyang Chemical Plant, Qingdao's system) boilings 10 hours, 120 ℃ of dryings, standby.Preparation contains the RhCl of 0.1 gram Rh
3Aqueous solution 25ml floods above-mentioned silica gel with this aqueous solution, seasoning, and 120 ℃ of oven dryings 4 hours, 300 ℃ of muffle furnace roastings 4 hours are at H
2Flow down in fixed bed and reduce, the reductive condition is: 300 ℃ of normal pressures, 1500h
-1, 4h treats after the reduction that temperature reduces under 200 ℃, purges 3h with catalyst deactivation with Ar, under the Ar protection catalyzer is preserved to the Sheleck bottle after reducing to room temperature.Example 2.
Take by weighing 10 gram gac almond charcoal (specific surface area 1182m
2/ g, pore volume 0.45cm
3/ g, flat footpath aperture 26.5 , Beijing brilliance timber mill system) boiling 10 hours, 120 ℃ of dryings, standby.Preparation contains the RhCl of 0.1 gram Rh
3(available from Johnson Matthey company) aqueous solution 25ml floods above-mentioned gac with this aqueous solution, seasoning, and 120 ℃ of oven dryings 4 hours are at H
2Flow down in fixed bed and reduce, the reductive condition is: 300 ℃ of normal pressures, 1500h
-1, 4h treats after the reduction that temperature reduces under 200 ℃, purges 3h with catalyst deactivation with Ar, under the Ar protection catalyzer is preserved to the Sheleck bottle after reducing to room temperature.Take by weighing 0.08 gram triphenylphosphine (TPP, ACROS corporate system), be dissolved in the 3.5ml hexanaphthene, with this solution impregnation in the good loaded metal sample of 1.5 gram reduction, fully shake 0.5h after, under the vacuum room temperature condition, take out 0.5h solvent drained.Example 3.
Get the reduction good metal rhodium catalyzer of 1.5 grams as using in the example 1, take by weighing 0.17 gram triphenylphosphine sodium trisulfonate (TPPTS, ACROS corporate system), be dissolved in 3.5ml water, this solution impregnation is restrained in the good sample of above-mentioned reduction 1.5, after fully shaking 0.5h, under the vacuum room temperature condition, take out 1h water is drained.Example 4.
Get the silica gel of 10 grams as using in the example 1.Take by weighing 0.256 gram RhClxH
2O and 0.126 gram VO (NO
3)
2Be dissolved in the 25ml water the above-mentioned silica gel of this aqueous solution stain stain, seasoning, 120 ℃ of oven dryings 4 hours, 300 ℃ of muffle furnace roastings 4 hours, H in the fixed bed
2Reduction, the reductive condition is: 300 ℃, normal pressure, 1500h
-1, 3h treats after the reduction that temperature reduces under 200 ℃, purges 3h with catalyst deactivation with Ar, sample is preserved to the Sheleck bottle after reducing to room temperature.Take by weighing 0.17 gram triphenylphosphine sodium trisulfonate (TPPTS), be dissolved in 3.5ml water, with this solution impregnation in the good sample of the 1.5 above-mentioned reduction of gram, fully shake 0.5h after, under the vacuum room temperature condition, take out 1h water drained.Example 5.
Get the reduction good metal rhodium catalyzer of 1.5 grams, take by weighing 0.08 gram triphenylphosphine (TPP), be dissolved in the 3.5ml hexanaphthene, this solution impregnation is restrained in the samples 1.5 as using in the example 1, fully shake 0.5h after, under the vacuum room temperature condition, take out 0.5h solvent drained.Example 6.
Get the reduction good metal rhodium catalyzer of 1.5 grams, take by weighing 0.475 gram, three phenolic group phosphines, be dissolved in the 3.5ml hexanaphthene, this solution impregnation is restrained in the samples 1.5 as using in the example 1, fully shake 0.5h after, under the vacuum room temperature condition, take out 0.5h solvent drained.Example 7.
Get 1.5 gram catalyzer in the example 1.Get 15ml 1-hexene and 60ml hexanaphthene respectively with syringe, weigh respectively.Hexanaphthene, 1-hexene and catalyzer are joined 300ml permanent magnetism successively stir in the stainless steel autoclave, after the sealing, with Ar gas (1.0MPa) displacement three times, use synthetic gas (H more earlier
2/ CO=1: 1,1.0Mpa) displacement is 3 times, charges into the 1.0MPa synthetic gas, and inspection was not warmed up to 373K after revealing in 1 hour, reaction under the 900r/min rotating speed stirs, reaction result is listed in the table 1..Example 8.
As the silica gel of using in the example 1, the dehydration degassing of finding time overnight under 120 ℃ of vacuum takes by weighing this silica gel 0.9 gram, and adds 0.55ml water, constantly shakes until silica gel the water that adds is evenly absorbed.Get 15ml water 1-hexene and 60ml hexanaphthene respectively with syringe, and weigh respectively.The catalyzer and the above-mentioned water silica gel that adds of hexanaphthene, 1-hexene, example 2 are joined in the 300ml permanent magnetism stirring stainless steel autoclave successively, after the sealing, with Ar gas (1.0Mpa) displacement three times, use synthetic gas (H more earlier
2/ CO=1: 1,1.0Mpa) displacement is 3 times, charges into the 1.0MPa synthetic gas, and inspection was not warmed up to 373K after revealing in 1 hour, reaction under the 900r/min rotating speed stirs, reaction result is listed in the table 1..Example 9.
As the silica gel of using in the example 1, the dehydration degassing of finding time overnight under 120 ℃ of vacuum takes by weighing this silica gel 0.9 gram, and adds the 0.55ml de-oxygenised water, constantly shakes until silica gel the water that adds is evenly absorbed.Get 1.67 gram catalyzer in the example 3.Get 15ml 1-hexene and 60ml hexanaphthene respectively with syringe, and weigh respectively.With hexanaphthene, 1-hexene, catalyzer with add water silica gel and join 300ml permanent magnetism successively and stir in the stainless steel autoclave, after the sealing, with Ar gas (1.0MPa) displacement three times, use synthetic gas (H more earlier
2/ CO=1: 1,1.0MPa) displacement is 3 times, charges into the 1.0MPa synthetic gas, and inspection was not warmed up to 373K after revealing in 1 hour, reaction under the 900r/min rotating speed stirs, reaction result is listed in the table 1..Example 10.
As the silica gel of using in the example 1, the dehydration degassing of finding time overnight under 120 ℃ of vacuum takes by weighing this silica gel 0.9 gram, and adds the 0.55ml de-oxygenised water, constantly shakes until silica gel the water that adds is evenly absorbed.Get 1.67 gram catalyzer in the example 4.Get 15ml 1-hexene and 60ml hexanaphthene respectively with syringe, and weigh respectively.With hexanaphthene, 1-hexene, catalyzer with add water silica gel and join 300ml permanent magnetism successively and stir in the stainless steel autoclave, after the sealing, with Ar gas (1.0Mpa) displacement three times, use synthetic gas (H more earlier
2/ CO=1: 1,1.0Mpa) displacement is 3 times, charges into the 1.0MPa synthetic gas, and inspection was not warmed up to 373K after revealing in 1 hour, reaction under the 900r/min rotating speed stirs, reaction result is listed in the table 1..Example 11.
Get 1.58 gram catalyzer in the example 5.Get 15ml 1-hexene and 60ml hexanaphthene respectively with syringe, and weigh respectively.Hexanaphthene, 1-hexene and catalyzer are joined 300ml permanent magnetism successively stir in the stainless steel autoclave, after the sealing, with Ar gas (1.0MPa) displacement three times, use synthetic gas (H more earlier
2/ CO=1: 1,1.0MPa) displacement is 3 times, charges into the 1.0MPa synthetic gas, and inspection was not warmed up to 373K after revealing in 1 hour, reaction under the 900r/min rotating speed stirs, reaction result is listed in the table 1..Example 12.
Get 1.975 gram catalyzer in the example 6.Get 15ml 1-hexene and 60ml hexanaphthene respectively with syringe, and weigh respectively.Hexanaphthene, 1-hexene and catalyzer are joined 300ml permanent magnetism successively stir in the stainless steel autoclave, after the sealing, with Ar gas (1.0MPa) displacement three times, use synthetic gas (H more earlier
2/ CO=1: 1,1.0MPa) displacement is 3 times, charges into the 1.0MPa synthetic gas, and inspection was not warmed up to 373K after revealing in 1 hour, reaction under the 900r/min rotating speed stirs, reaction result is listed in the table 1..Example 13.
Get 1.58 gram catalyzer in the example 5.Get the 60ml hexanaphthene with syringe, and weigh.Catalyzer and 60ml hexanaphthene are joined in the 300ml permanent magnetism stirring stainless steel autoclave, after the sealing, with Ar gas (1.0MPa) displacement three times, use gas mixture (C more earlier
2H
2/ H
2/ CO=1: 1: 1; 1.0MPa) replace 3 times, charging into the 1.0MPa gas mixture, inspection was not warmed up to 373K, air speed 2800h after revealing in 1 hour
-1, reaction under the 900r/min rotating speed stirs, reaction result is listed in the table 1..
Table 1. heterogeneous catalyst, even phase catalyst and the even hydroformylation reaction performance of changing heterogeneous catalyst mutually
Reaction conditions: T=100 ℃, P=1.0MPa, t=4hr, R=900r/min, 15ml 1-hexene, 60ml hexanaphthene; * t=2hr, * * reactant: ethene
| Catalyzer | Total conversion rate wt.% | Selectivity | ??TOF??h -1 | |||
| Aldehyde, wt.% | Normal hexane wt.% | 2 hexenes, 3-hexene wt.% | ??n/i | |||
| Example 1 | ??97.5 | ????6.92 | ????0 | ????93.08 | ????1.1 | ????20.8 |
| Example 2 | ??39.1 | ????87.9 | ????3.46 | ????8.64 | ????9.0 | ????256.1 |
| Example 3 | ??12.76 | ????74.76 | ????10.66 | ????14.66 | ????8.83 | ????35.58 |
| Example 4 | ??27.77 | ????88.04 | ????5.47 | ????5.37 | ????6.59 | ????91.2 |
| Example 5 | ??99.7 | ????92.9 | ????1.79 | ????5.28 | ????2 | ????680.0 |
| Example 6* | ??94.85 | ????76.08 | ????2.4 | ????21.5 | ????4.74 | ????1058.2 |
| Example 5** | ??90 | ????99.5 | ????0.5 | ????- | ????- | ????2010.4 |
By above-mentioned result as can be known; utilize the even system of changing mutually of heterogeneous catalyst of the present invention; for example on silicon dioxide carried rhodium catalyst, flood organic ligand; triphenylphosphine; sulfonated triphenylphosphine or three phenolic group phosphines etc. are made catalyzer; in paste state bed reactor, carry out gap or successive hydroformylation of olefin; with the condition of corresponding even mutually catalytic gentleness under; its catalytic activity and even phase catalyst are basic identical, i.e. catalytic activity height, the highest can be near 100%; highly selective is good; can be near 100%, the separation of catalyzer gets final product by simple filtering, and catalyzer is reusable.This catalyzer that can be used for producing by olefin hydroformylation in the industrial production all kinds of organic aldehydes by the even change method mutually of heterogeneous catalyst.
Claims (10)
1, a kind of catalyzer of producing all kinds of organic aldehydes by olefin hydroformylation, it is characterized in that, this catalyzer comprises active ingredient, auxiliary agent, carrier and even phase catalyst part four parts, active ingredient is metal Rh, Pt, Ru or Pd, auxiliary agent is Nb, Ta, Ti, Zr, Hf, Mn, Tc or Re, carrier is selected silicon-dioxide, MCM-41, gac or aluminium sesquioxide for use, organic even phase catalyst part is selected triphenylphosphine for use, the triphenylphosphine sodium trisulfonate, triphenylphosphine oxide, three cyclohexyl phosphines or three phenolic group phosphines; And active ingredient accounts for 0.01-5.0% in total catalyst weight, auxiliary element accounts for 0.01-10.0% in total catalyst weight, and the gross weight of organic even phase catalyst part in catalyzer is 0.01-30.0%.
2, according to the described catalyzer of claim 1, it is characterized in that: main reactive metal accounts for 0.01-1.0% in total catalyst weight.
3, according to the described catalyzer that is used for of claim 1, it is characterized in that: the specific surface area of described carrier is 150m
2/ g-400m
2/ g, pore volume are 0.5-2.0cm
3/ g, pore size distribution are 4-1000 .
4, according to the described catalyzer of claim 1, it is characterized in that: auxiliary element accounts for 0.1-5.0% in total catalyst weight.
5, according to the described catalyzer of claim 1, it is characterized in that: the gross weight of organic even phase catalyst part in catalyzer is 1.0-20.0%.
6, according to the described catalyzer of claim 1-5, it is characterized in that: active ingredient is a rhodium, and auxiliary agent is V, and carrier is a silicon-dioxide, is triphenylphosphine or triphenylphosphine sodium trisulfonate and the homogeneous phase catalyst ligand is arranged.
7, a kind of claim 1 is described produces the Preparation of catalysts method of all kinds of organic aldehydes by olefin hydroformylation, it is characterized in that:
1) aqueous solution with the solubility salt of active ingredient and all auxiliary elements adopts pickling process, be immersed on the above-mentioned carrier, and drying, normal pressure hydrogen reducing, reduction temperature are 100-600 ℃, the recovery time is to obtain heterogeneous catalyst in 1-30 hour;
2) in the phosphine ligand solution of even phase catalyst, adopt conventional pickling process, be immersed on the above-mentioned heterogeneous catalyst, the drying of finding time removes solvent and obtains catalyzer.
8, according to the described catalyzer of claim 6, it is characterized in that: the solubility salt is nitrate or carbonyl compound.
9, according to the described catalyzer of claim 6, it is characterized in that: the phosphine part is a triphenylphosphine, triphenylphosphine sodium trisulfonate, triphenylphosphine oxide, three cyclohexyl phosphines or three phenolic group phosphines, when the phosphine part is triphenylphosphine (TPP), triphenylphosphine oxide, three cyclohexyl phosphines or during at the phenolic group phosphine, dissolve with organic solvent, used organic solvent can use pentane, hexane or hexanaphthene; And the phosphine part is when being the triphenylphosphine sodium trisulfonate, and water dissolves.
10, the described catalyzer of a kind of claim 1 is used for producing all kinds of organic aldehyde reactions by olefin hydroformylation.
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| CN101116816B (en) * | 2007-07-03 | 2010-08-18 | 中国石油大学(华东) | Method for preparing load type rhodium catalyst for making high-carbon aldehyde using hydroformylation of higher olefins |
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| CN115672407A (en) * | 2022-11-23 | 2023-02-03 | 中国石油大学(华东) | Phosphine ligand modified carbon-supported monatomic rhodium catalyst and preparation and application methods thereof |
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2001
- 2001-12-06 CN CNB011404345A patent/CN1151888C/en not_active Expired - Fee Related
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| CN101116816B (en) * | 2007-07-03 | 2010-08-18 | 中国石油大学(华东) | Method for preparing load type rhodium catalyst for making high-carbon aldehyde using hydroformylation of higher olefins |
| CN101642719B (en) * | 2008-08-07 | 2012-08-22 | 中国科学院大连化学物理研究所 | Anchor ligand modified metal supported catalyst and preparation method and application thereof |
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| CN104874423B (en) * | 2014-02-27 | 2017-03-22 | 中国石油化工股份有限公司 | Preparation method of bimetallic catalyst containing rhodium and ruthenium |
| CN104874423A (en) * | 2014-02-27 | 2015-09-02 | 中国石油化工股份有限公司 | Preparation method of bimetallic catalyst containing rhodium and ruthenium |
| CN107236005A (en) * | 2017-06-29 | 2017-10-10 | 管德新 | The synthetic method and its application process of a kind of co-catalyst available for hydroformylation |
| CN108080030A (en) * | 2017-12-21 | 2018-05-29 | 江苏欣诺科催化剂有限公司 | A kind of immobilized method of olefin hydroformylation catalyst |
| CN109046465A (en) * | 2018-07-25 | 2018-12-21 | 华东师范大学 | The preparation and application of a kind of immobilized chiral Au catalyst of mesoporous silicon material |
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| CN113351249A (en) * | 2021-04-29 | 2021-09-07 | 四川大学 | Catalytic system for preparing aldehyde by catalyzing hydroformylation of internal olefin |
| CN113351249B (en) * | 2021-04-29 | 2023-02-03 | 四川大学 | Catalytic system for preparing aldehyde by catalyzing hydroformylation of internal olefin |
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| CN115672407A (en) * | 2022-11-23 | 2023-02-03 | 中国石油大学(华东) | Phosphine ligand modified carbon-supported monatomic rhodium catalyst and preparation and application methods thereof |
| CN115672407B (en) * | 2022-11-23 | 2024-02-02 | 中国石油大学(华东) | Phosphine ligand modified carbon-supported monoatomic rhodium catalyst and preparation and application methods thereof |
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