CN109456154A - A method of fatty aldehyde is prepared by hydroformylation reaction - Google Patents
A method of fatty aldehyde is prepared by hydroformylation reaction Download PDFInfo
- Publication number
- CN109456154A CN109456154A CN201811358143.4A CN201811358143A CN109456154A CN 109456154 A CN109456154 A CN 109456154A CN 201811358143 A CN201811358143 A CN 201811358143A CN 109456154 A CN109456154 A CN 109456154A
- Authority
- CN
- China
- Prior art keywords
- butylene
- reaction
- rhodium
- water
- phosphine ligands
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
Abstract
The invention discloses a kind of methods for preparing fatty aldehyde by hydroformylation reaction; using the catalyst system of Water-soluble rhodium complexes and biphosphine ligand composition in water/organic two-phase; it is catalyzed 1- butylene; 2- butylene and their mixture carry out hydroformylation reaction and prepare valeraldehyde; using the combination of water-soluble biphosphine ligand BISBIS and organic additive; promote butene hydroformylation reaction to accelerate, generates valeraldehyde/foreign matter aldehyde molar ratio and be greater than 93: 7.Catalyst aqueous solution separates simplicity, and stable in catalytic performance with product, and reaction condition mitigates, and catalyst long service life significantly reduces the production cost of valeraldehyde.
Description
Technical field
The present invention relates to fatty aldehyde preparation technical fields, prepare fatty aldehyde more particularly to hydroformylation reaction.
Background technique
Butene hydroformylation prepares the important channel that valeral is C4 alkene comprehensive utilization of resources.It can be prepared from valeral
The intermediate and fine chemicals that a series of organic syntheses need: valeral adds hydrogen that can produce amylalcohol, valeral through bimolecular condensation and
Add hydrogen that can prepare isodecanol, this is the advanced plasticizer institute that recent domestic is very paid close attention to and the production of active development is excellent
The optimal path of the isodecanol needed.
Both at home and abroad using 1- butylene as raw material through hydroformylation reaction generate valeraldehyde based on product there are many report, but
It is that valeral is prepared by 1- butylene since the price of pure 1- butylene is much higher more than the mixture price of 1- butylene and 2- butylene
Cost it is very high.The butylene produced in present petroleum refining process is butylene containing 1-, and the mixture of 2- butylene and isobutene passes through
Isobutene conversion therein can be methyl tertiary butyl ether(MTBE) (MTBE), be used as gasoline additive, remain by the etherification reaction of it and methanol
The isolated mixing for containing a small amount of isobutene and butane based on 1- butylene and 2- butylene that remaining component passes through alkene and alkane
Object (referred to as " mixed butene ").If producing valeral using this mixture as raw material by hydroformylation, can not only making Butene
It is fully used, and raw material abundant can be provided to produce the plasticizer of excellent performance, obtain higher economic benefit.
Since 2- butylene purposes is limited, and its content ratio 1- butylene in mixed butene is much higher, using present industry
Rhodium used in production/triphenylphosphine catalysis system is difficult to convert valeral by hydroformylation reaction for 2- butylene.Therefore,
Both at home and abroad to using 1- butylene and 2- butene mixture as raw material by hydroformylation reaction synthesize valeral new catalyst system and
Reaction process has conducted extensive research, developed for mixed butylene hydroformylation prepare valeral homogeneous catalyst system and
New reaction process.Patent CN100412046C disclose with rhodium/bi-phosphoramide catalyst system homogeneous catalysis 1- butylene with
The method that 2- butene mixture hydroformylation prepares valeral, CN1993311B are disclosed with rhodium/bis-phosphite catalyst system
The method that homogeneous catalysis 1- butylene and 2- butene mixture hydroformylation prepare valeral.The butylene hydrogen as described in above-mentioned patent
Formyl turns to homogeneous catalysis technique, and in reaction system after the reaction was completed, catalyst and product valeral are in organic phase together, will
Rhodium catalyst is separated and is recycled with product, is all after being steamed product using distillating method, then catalyst solution is recycled
Reactor is returned, and the boiling point for the valeral that butene hydroformylation generates is more taller than the boiling point for the butyraldehyde that hydroformylation of propene generates,
Higher temperature is needed when distillation separation, will cause separating energy consumption height, the generation of valeral condensation product increases, and catalyst separates
Also need regeneration activating processing that could be recycled afterwards, this will lead to rhodium complex and Phosphine ligands and damages in separation and regenerative process
It loses, increases the consumption of catalyst and Phosphine ligands, while making production process complicated, producing cost increases.In addition, double Asias
Phosphate and bi-phosphoramide preparation process are complicated, expensive, and stability is poor in use process, easy to oxidize and water
Solution, the easy gelation of alkyl hydroxy phosphonic acids generated of degrading easily cause catalyst recycle process line clogging, therefore when reaction
It must take appropriate measures, and strictly remove micro amount of oxygen and water, to ensure its catalyst performance stabilised, this also considerably increases whole
The complexity of a technical process.In addition, be to accelerate 2- butene hydroformylation reaction speed during homogeneous catalysis, the conjunction of use
At H in gas2The molar ratio of/CO is up to 2: 1~25: 1, and the amount that this can make butylene be hydrogenated to butane is more, causes Butene
It is underutilized.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing fatty aldehyde by hydroformylation reaction, this method passes through
Biphase catalytic system, can directly adopt the 1- butylene produced in petroleum refining process, 2- butylene and contain a small amount of isobutene and fourth
The mixture of alkane synthctic fat aldehyde under low pressure.
Included at least the present invention provides a kind of method for preparing fatty aldehyde by hydroformylation reaction, in reaction system with
One of water-soluble phosphine ligand A Phosphine ligands of flowering structure formula:
Wherein, R is selected from H, CH3Or OCH3。
Further, the water-soluble phosphine ligand of following structural formula is included at least in reaction system:
Further, the water-soluble phosphine ligand further includes B Phosphine ligands, the B Phosphine ligands be following compounds at least
It is a kind of:
The addition meeting of above-mentioned four kinds of ligands is so that the selectivity and yield of reaction are further enhanced.Wherein, TPPDS,
The synthesis step of tri- kinds of ligands of TPPMS and SLPTS-3 is relatively complicated, therefore, in production application, preferably TPPTS come into
Row reaction, to improve production efficiency and reduce production cost.In an embodiment of the present invention, BISBIS and TPPTS two are mostly used
Kind ligand is that optimum reaction condition is tested.
Further, the method includes the following steps:
(1) reactor is added in rhodium catalyst, A Phosphine ligands and/or B Phosphine ligands, organic additive and water；
(2) air in reactor is displaced with nitrogen, then reactor is added in olefin feedstock, synthesis gas, 100~
150 DEG C, gross pressure be 1.5~5.0MPa under the conditions of react 1~8h.
Further, A Phosphine ligands: the molar ratio of B Phosphine ligands is 3: 1~20: 1；A Phosphine ligands: Rh is (in old catalyst
Rhodium) molar ratio be 5: 1~20: 1.
Further, concentration of the rhodium in the rhodium catalyst in water phase is 200ppm~400ppm；The synthesis gas
The molar ratio of middle hydrogen and carbon monoxide is 1: 1~1.5: 1；The volume ratio of the water and organic additive is 5: 1~5: 3.
Further, the rhodium catalyst be selected from rhodium compound, rhodium complex, be further selected from rhodium chloride, rhodium acetate,
Rhodium nitrate, RhCl (TPPTS)3、RhCl(CO)(TPPTS)2、HRh(CO)(TPPTS)3、HRh(CO)2One of BISBIS or
It is several.
Rhodium catalyst used in the method for the present invention is selected from compound, rhodium complex, refers to, rhodium catalyst can be rhodium
Compound is also possible to that the rhodium complex for having ligand is complexed in advance, can also be that the compound of rhodium and complexing in advance have ligand
The mixed catalyst of rhodium complex.
Further, the olefin feedstock is selected from C3~C20Alkene；It is further C3~C5Alkene is further selected from
1- butylene and/or 2- butylene.
Olefin feedstock used in the method for the present invention can be 1- alkene, be also possible to 2- alkene, can also be 1- alkene
With the mixture of 2- alkene.
Further, organic additive is selected from one or more of aldehydes, ethers, alkyl benzene, alkane derivative；Into
One step, the ethers is selected from one or more of methyl phenyl ethers anisole, phenetole, polyethoxy ether；Further, the alkylbenzene
Class is selected from one or more of toluene, dimethylbenzene；Further, alkanes are selected from hexamethylene, hexahydrotoluene, heptane, pungent
One or more of alkane.
Further, the olefin feedstock is impure mixed olefins, wherein linear alkene needed for participating in reaction
Total content is not less than 60%wt.
Further, the olefin feedstock is impure mixed butene, wherein the total content of 1- butylene and 2- butylene is not
Lower than 80%wt.
Further, the impurity composition is butane and isobutene.
Olefin feedstock used in the method for the present invention, can be containing a small amount of other industrial impurity, for example may come from stone
C in oil refining production process4Component is also possible to the C of methanol-to-olefins process generation4During component or Fischer-Tropsch coal oil
The C of generation4Component, the present invention directly can carry out industrial production as raw material, not influence yield and product quality.In the present invention
Specific embodiment in, contain a small amount of isobutyl obtained in the petroleum refining process that directly uses based on 1- butylene and 2- butylene
The mixture of alkene and butane is raw material, can obtain valeraldehyde with highly selective and excellent yield.
Further, reaction temperature is 110~140 DEG C, reaction pressure is 2~4MPa, and the reaction time is 2~5h.
The beneficial effects of the present invention are:
(1) 1- butylene or 2- butylene can be selected in the method raw material that the present invention prepares fatty aldehyde, can also directly select different works
The 1- butylene that skill process source obtains, 2- butylene and the mixture containing a small amount of isobutene and butane generate valeraldehyde in valeral and contain
For amount up to 95% or more, selectivity is good, resource can be made to be fully used, reduce production cost, simplify processing step.
(2) the method for the present invention prepares fatty aldehyde using biphase catalytic system, selects water-soluble rhodium complex compound and water solubility double
The aqueous solution of Phosphine ligands is as catalyst, and rhodium catalyst and biphosphine ligand can lead to aqueous solution in water phase after the reaction was completed
It crosses with after organic product phase liquid-liquid separation, is directly reused in return autoclave, be not necessarily to high temperature distillation and activating and regenerating, energy
It consumes low, the loss of rhodium complex and Phosphine ligands in process of production can be reduced, catalyst activity and selectivity can be preferably kept,
Simplify production process, reduces production cost.
(3) Phosphine ligands stability used in the method for the present invention is good, and anti-poisoning capability is strong, not oxidizable and hydrolysis, reaction
Without harsh stringent waterless operation, entire technical process is enormously simplified.Wherein, 2, the 2- dimethylene of preparation easy to use
Biphenyl (diphenylphosphine) sulfonate sodium (BISBIS) and the m- trisulfonic acid sodium salt (TPPTS) of triphenylphosphine-are used as optimum condition, at
This is cheap, is suitble to large-scale industrial production.
(4) the method for the present invention reaction speed is fast, only need 2~5h can fully reacting, H in synthesis gas2The molar ratio of/CO is only
1: 1~1.5: 1 is needed, without high H2/ CO molar ratio has also achieved the effect that fast reaction, can effectively reduce butylene and add hydrogen
Generate the generation of the side reactions such as butane.
(5) 2~4MPa of reaction pressure of the method for the present invention is not necessarily to high pressure, realizes effective low pressure carbonylation synthesis
Technique can reduce manufacturing cost and maintenance cost to production equipment, better ensure that the safety of production.
Specific embodiment
Ligand used in the embodiment of the present invention is commercially available or is synthesized according to conventional method in that art.
Embodiment 1
500mL water, 100mL valeraldehyde and 100mL polyethoxy ether HO- (- CH are added into 1 liter of autoclave2CH2O)4CH2CH2Then rhodium complex HRh (CO) (TPPTS) is added in OH3, BISBIS and TPPTS reach rhodium concentration in aqueous solution
The molar ratio that the molar ratio of 300ppm, BISBIS/Rh are 15: 1, BISBIS/TPPTS is 6: 1, and nitrogen is introduced after being stirred and is set
Air 3 times in kettle are changed, the mixing fourth for being 21%: 79% by the ratio of 1- butylene and 2- butylene by feed pump after reaction kettle is evacuated
Alkene 70g is added in reaction kettle, then by H2: the synthesis gas of CO=1.1: 1 molar ratio is added in kettle by high pressure gas cylinder, in reaction temperature
120 DEG C, 400 revs/min of mixing speed, 3h is reacted under pressure 2.5MPa constant pressure in kettle, then water flowing cooling reaches temperature in the kettle
Reaction gas reactor emptying is taken out total overall reaction liquid, is divided into liquid clear can be observed two layers by room temperature, and upper layer is colourless
Transparent organic phase, lower layer are yellow catalyst solution, and organic phase measures mixed butene conversion ratio through gas chromatographic analysis
80%, the selectivity 92% of valeral, the ratio between valeraldehyde and isopentyl aldehyde 29: 1 are generated, remaining product is n-amyl alcohol 7.5%, condensation product
0.5%.
Embodiment 2
Mixed butylene hydroformylation reaction is carried out as described in Example 1, the difference is that the rhodium complex used
For RhCl (TPPTS)3, organic additive is 50mL methyl phenyl ethers anisole and 150mL polyethoxy ether HO- (- CH2CH2O)8CH2CH2OH, it is water-soluble
Rhodium concentration is 200ppm in liquid, and the molar ratio that the molar ratio of BISBIS/Rh is 10: 1, BISBIS/TPPTS is 8: 1, reacts 3h,
Mixed butene conversion ratio 75%, generates the selectivity 93% of valeral, the ratio between valeraldehyde and isopentyl aldehyde 22: 1, remaining product is positive penta
Alcohol 6.1%, condensation product 0.9%.
Embodiment 3
Mixed butylene hydroformylation reaction is carried out as described in Example 1, the difference is that the rhodium complex used
For HRh (CO)2(BISBIS), rhodium concentration is 400ppm in aqueous solution, and organic additive is toluene and each 100mL of valeraldehyde.Reaction
4h, mixed butene conversion ratio 83% generate the selectivity 93% of valeral, the ratio between valeraldehyde and isopentyl aldehyde 25: 1, remaining product is
N-amyl alcohol 6.3%, condensation product 0.7%.
Embodiment 4
Mixed butylene hydroformylation reaction is carried out as described in Example 1, the difference is that the mixed butene used
Ratio be 1- butylene 15%, 2- butylene 83%, butane 2%, organic additive be valeraldehyde 100mL and hexahydrotoluene 80mL.
4h is reacted, mixed butene conversion ratio 73% generates the selectivity 92% of valeral, the ratio between valeraldehyde and isopentyl aldehyde 21: 1, remaining production
Object is n-amyl alcohol 7.3%, condensation product 0.7%.
Embodiment 5
Mixed butylene hydroformylation reaction is carried out as described in Example 1, the difference is that the mixed butene used
Ratio be 1- butylene 5%, 2- butylene 92%, isobutene 1%, butane 2%, react 3h, mixed butene conversion ratio 76%, generate
The selectivity 92% of valeral, the ratio between valeraldehyde and isopentyl aldehyde 17: 1, remaining product are n-amyl alcohol 6.8%, condensation product 1.2%.
Embodiment 6
Butene hydroformylation reaction is carried out as described in Example 1, the difference is that TPPTS is not added, BISBIS/
The molar ratio of Rh is 12: 1, uses the 2- butylene of content 99% for raw material, reacts 3h, and 2- butene conversion 73% generates valeral
Selectivity 94%, the ratio between valeraldehyde and isopentyl aldehyde 32: 1, remaining product be n-amyl alcohol 5.2%, condensation product 0.8%.
Embodiment 7
Mixed butylene hydroformylation reaction is carried out by the condition of embodiment 1, the difference is that with shown in Formula II structure
Phosphine ligands (R=H) replace BISBIS, synthesis gas (H2: CO=1.5: 1v/v), pressure 3.0MPa, 150 DEG C of reaction temperature.It is mixed
Butene conversion 78% is closed, the selectivity 93% of valeral, the ratio between valeraldehyde and isopentyl aldehyde 31: 1 are generated, remaining product is n-amyl alcohol
7.3%, condensation product 0.7%.
Embodiment 8
Mixed butylene hydroformylation reaction is carried out by the condition of embodiment 1, the difference is that with Phosphine ligands TPPDS generation
The molar ratio that molar ratio for TPPTS, BISBIS and TPPDS is 20: 1, BISBIS/Rh is 5: 1, synthesis gas (H2: CO=1.1:
1v/v) pressure be 1.5MPa, 100 DEG C of reaction temperature,.Mixed butene conversion ratio 65%, generates the selectivity 96% of valeral, and positive penta
The ratio between aldehyde and isopentyl aldehyde 28: 1, remaining product are n-amyl alcohol 3.5%, condensation product 0.5%.
Embodiment 9
Mixed butylene hydroformylation reaction is carried out by the condition of embodiment 1, the difference is that with Phosphine ligands TPPMS generation
For TPPTS, the molar ratio of BISBIS/Rh is 20: 1, synthesis gas (H2: CO=1.2: 1v/v) pressure is 5.0MPa.Mixed butene
Conversion ratio 84% generates the selectivity 95% of valeral, the ratio between valeraldehyde and isopentyl aldehyde 31: 1, remaining product is n-amyl alcohol 4.7%,
Condensation product 0.3%.
Embodiment 10
Mixed butylene hydroformylation reaction is carried out by the condition of embodiment 1, the difference is that with Phosphine ligands SLPTS-3
Molar ratio instead of TPPTS, BISBIS and SLPTS-3 is 3: 1, synthesis gas (H2: CO=1.2: 1v/v) pressure is 4.0MPa, instead
8h between seasonable.Mixed butene conversion ratio 85%, generates the selectivity 92% of valeral, the ratio between valeraldehyde and isopentyl aldehyde 29: 1, remaining
Product is n-amyl alcohol 7.4%, condensation product 0.6%.
Embodiment 11
As described in Example 1 carry out mixed butylene hydroformylation reaction, the difference is that use organic additive for
50mL methyl phenyl ethers anisole and 170mL polyethoxy ether HOCH2CH2OCH2CH2OH, rhodium concentration is 250ppm, BISBIS/Rh in aqueous solution
Molar ratio be 13: 1, do not add TPPTS, react 1h, mixed butene conversion ratio 71% generates the selectivity 93% of valeral, just
The ratio between valeral and isopentyl aldehyde 35: 1, remaining product are n-amyl alcohol 6.4%, condensation product 0.6%.
Embodiment 12
Mixed butylene hydroformylation reaction is carried out by the condition of embodiment 1, examines or check the shadow of the variation of reaction temperature and pressure
Ring, experiment condition and the results are shown in Table 1, selectivity of product such as 2 institute of table not:
Table 1
2. selectivity of product of table
Embodiment 13
Mixed butylene hydroformylation reaction is carried out as described in Example 1, and the catalyst isolated after being reacted is water-soluble
Liquid is recycled back to reaction kettle, carries out catalyst stability investigation, proves by 500h circulation experiment, and the performance of catalyst is stablized, and mixes
The conversion ratio for closing butylene is 78%~81%, generates the selectivity 92%~94% of valeral, and the ratio between valeraldehyde and isopentyl aldehyde are 25:
1~31: 1, remaining product is n-amyl alcohol 5.5%~7.2%, and condensation product is 0.5%~0.8%.
According to the experimental results, the catalyst stability of the method for the present invention is good, still has good catalysis after circulation is multiple
Activity and selectivity, performance are stablized, this is because the method for the present invention when catalyst is recycled, is not necessarily to high temperature distillation and activation
Processing will directly be reused in water phase Returning reacting system.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (10)
1. a kind of method for preparing fatty aldehyde by hydroformylation reaction, which is characterized in that included at least in reaction system following
One of water-soluble A Phosphine ligands of general structure:
Wherein, R is selected from H, CH3Or OCH3。
2. the method according to claim 1, wherein including at least the water solubility of following structural formula in reaction system
Phosphine ligands:
3. the method according to claim 1, wherein the water-soluble phosphine ligand further includes B Phosphine ligands, the B
Phosphine ligands are at least one of following compounds:
4. described in any item methods according to claim 1~3, characterized in that it comprises the following steps:
(1) reactor is added in rhodium catalyst, A Phosphine ligands and/or B Phosphine ligands, organic additive and water；
(2) displace the air in reactor with nitrogen, then reactor be added in olefin feedstock, synthesis gas, 100~150 DEG C,
Gross pressure reacts 1~8h under the conditions of being 1.5~5.0MPa.
5. method according to claim 4, which is characterized in that A Phosphine ligands: the molar ratio of B Phosphine ligands is 3: 1~20: 1；A phosphine
Ligand: the molar ratio of Rh is 5: 1~20: 1；Concentration of the rhodium in water phase in the rhodium catalyst is 200ppm~400ppm；
The molar ratio of hydrogen and carbon monoxide is 1: 1~1.5: 1 in the synthesis gas；The volume ratio of the water and organic additive is 5: 1
~5: 3.
6. method according to claim 4, which is characterized in that the rhodium catalyst is selected from rhodium compound, rhodium complex, into one
Step is selected from rhodium chloride, rhodium acetate, rhodium nitrate, RhCl (TPPTS)3、RhCl(CO)(TPPTS)2、HRh(CO)(TPPTS)3、HRh
(CO)2One or more of BISBIS.
7. according to the method described in claim 4, it is characterized in that, the olefin feedstock is selected from C3~C20Alkene；It is further C3
~C5Alkene is further selected from 1- butylene and/or 2- butylene.
8. according to the method described in claim 4, it is characterized in that, the organic additive be selected from aldehydes, ethers, alkyl benzene,
One or more of alkane derivative；Further, the ethers is in methyl phenyl ethers anisole, phenetole, polyethoxy ether
It is one or more of；Further, the alkyl benzene is selected from one or more of toluene, dimethylbenzene；Further, alkanes
Selected from one or more of hexamethylene, hexahydrotoluene, heptane, octane.
9. the method according to the description of claim 7 is characterized in that the olefin feedstock is impure mixed olefins, wherein
The total content of linear alkene needed for participating in reaction is not less than 60wt%；Further, the olefin feedstock is impure mixes
Close butylene, wherein the total content of 1- butylene and 2- butylene is not less than 80%wt.
10. according to the method described in claim 4, it is characterized in that, reaction temperature be 110~140 DEG C, reaction pressure be 2~
4MPa, reaction time are 2~5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811358143.4A CN109456154A (en) | 2018-11-14 | 2018-11-14 | A method of fatty aldehyde is prepared by hydroformylation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811358143.4A CN109456154A (en) | 2018-11-14 | 2018-11-14 | A method of fatty aldehyde is prepared by hydroformylation reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109456154A true CN109456154A (en) | 2019-03-12 |
Family
ID=65610542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811358143.4A Pending CN109456154A (en) | 2018-11-14 | 2018-11-14 | A method of fatty aldehyde is prepared by hydroformylation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109456154A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606792A (en) * | 2020-06-29 | 2020-09-01 | 成都欣华源科技有限责任公司 | Method for preparing high-carbon aldehyde |
| CN112225654A (en) * | 2020-11-02 | 2021-01-15 | 中国海洋石油集团有限公司 | Device and method for comprehensively utilizing mixed C4 |
| CN113121614A (en) * | 2021-04-22 | 2021-07-16 | 中国科学院上海高等研究院 | Water-soluble metal-based complex and preparation method and application thereof |
| CN113402552A (en) * | 2021-07-21 | 2021-09-17 | 成都欣华源科技有限责任公司 | Catalyst for preparing aldehyde compound by hydroformylation of vegetable oil and method thereof |
| CN113559932A (en) * | 2021-06-30 | 2021-10-29 | 中国成达工程有限公司 | Catalyst system for synthesizing butanedialdehyde from acrolein hydroformylation |
| CN114621067A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | High-value utilization method of carbon-tetracarbon |
| CN115141090A (en) * | 2021-03-29 | 2022-10-04 | 中国石油化工股份有限公司 | Preparation method of olefine aldehyde |
| CN115141090B (en) * | 2021-03-29 | 2024-05-17 | 中国石油化工股份有限公司 | Preparation method of enal |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4694109A (en) * | 1986-06-13 | 1987-09-15 | Eastman Kodak Company | Chelate ligands for low pressure hydroformylation catalyst and process employing same |
| US5274183A (en) * | 1990-12-17 | 1993-12-28 | Hoechst Aktiengesellschaft | Water-soluble sulfonated diphosphines |
| CN1272485A (en) * | 1999-04-29 | 2000-11-08 | 中国石油化工集团公司 | Preparation method of aldehyde |
| CN1434015A (en) * | 2002-01-25 | 2003-08-06 | 四川大学 | Process for preparing propionaldehyde from ethylene |
| CN1527834A (en) * | 2001-03-26 | 2004-09-08 | �¿�ɭŵ���շһ�ѧ�ɷ�����˾ | Method for producing diphosphines and the use thereof |
| CN101288852A (en) * | 2008-04-29 | 2008-10-22 | 上海焦化有限公司 | Catalyst composition for reaction of hydroformylation of propene, |
| CN102826976A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for adjusting ratio of butyraldehyde to isobutyraldehyde in propylene catalytic preparation |
| CN102911021A (en) * | 2012-11-12 | 2013-02-06 | 青岛三力本诺化学工业有限公司 | Method for preparing aldehyde through linear chain olefin hydroformylation |
| CN105566081A (en) * | 2015-12-15 | 2016-05-11 | 上海华谊（集团）公司 | Method for preparing aldehyde through olefin hydroformylation |
| CN105732727A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of bidentate phosphine rhodium complex, bidentate phosphine rhodium complex and application thereof |
| CN106000470A (en) * | 2016-06-06 | 2016-10-12 | 四川大学 | Catalyst used for hydroformylation of olefin, and preparation method and application thereof |
| CN106083551A (en) * | 2016-06-30 | 2016-11-09 | 成都欣华源科技有限责任公司 | A kind of hydroformylation of propene prepares the method for butyraldehyde |
| CN107597192A (en) * | 2017-09-15 | 2018-01-19 | 万华化学集团股份有限公司 | A kind of catalyst and hydroformylation reaction method for hydroformylation reaction |
-
2018
- 2018-11-14 CN CN201811358143.4A patent/CN109456154A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4694109A (en) * | 1986-06-13 | 1987-09-15 | Eastman Kodak Company | Chelate ligands for low pressure hydroformylation catalyst and process employing same |
| US5274183A (en) * | 1990-12-17 | 1993-12-28 | Hoechst Aktiengesellschaft | Water-soluble sulfonated diphosphines |
| CN1272485A (en) * | 1999-04-29 | 2000-11-08 | 中国石油化工集团公司 | Preparation method of aldehyde |
| CN1527834A (en) * | 2001-03-26 | 2004-09-08 | �¿�ɭŵ���շһ�ѧ�ɷ�����˾ | Method for producing diphosphines and the use thereof |
| CN1434015A (en) * | 2002-01-25 | 2003-08-06 | 四川大学 | Process for preparing propionaldehyde from ethylene |
| CN101288852A (en) * | 2008-04-29 | 2008-10-22 | 上海焦化有限公司 | Catalyst composition for reaction of hydroformylation of propene, |
| CN102826976A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for adjusting ratio of butyraldehyde to isobutyraldehyde in propylene catalytic preparation |
| CN102911021A (en) * | 2012-11-12 | 2013-02-06 | 青岛三力本诺化学工业有限公司 | Method for preparing aldehyde through linear chain olefin hydroformylation |
| CN105732727A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of bidentate phosphine rhodium complex, bidentate phosphine rhodium complex and application thereof |
| CN105566081A (en) * | 2015-12-15 | 2016-05-11 | 上海华谊（集团）公司 | Method for preparing aldehyde through olefin hydroformylation |
| CN106000470A (en) * | 2016-06-06 | 2016-10-12 | 四川大学 | Catalyst used for hydroformylation of olefin, and preparation method and application thereof |
| CN106083551A (en) * | 2016-06-30 | 2016-11-09 | 成都欣华源科技有限责任公司 | A kind of hydroformylation of propene prepares the method for butyraldehyde |
| CN107597192A (en) * | 2017-09-15 | 2018-01-19 | 万华化学集团股份有限公司 | A kind of catalyst and hydroformylation reaction method for hydroformylation reaction |
Non-Patent Citations (4)
| Title |
|---|
| 付海燕等: "水溶性铑膦配合物催化烯烃氢甲酰化反应研究进展", 《催化学报》 * |
| 张寿春等: "铑-膦配位催化烯烃氢甲酰化反应研究", 《化学研究与应用》 * |
| 李贤均等: "水溶性铑膦络合物催化低碳烯烃氢甲酰化合成醛的清洁生产技术", 《石油化工》 * |
| 陈华等: "烯烃氢甲酰化反应研究进展", 《化学研究与应用》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606792A (en) * | 2020-06-29 | 2020-09-01 | 成都欣华源科技有限责任公司 | Method for preparing high-carbon aldehyde |
| CN111606792B (en) * | 2020-06-29 | 2023-02-03 | 成都欣华源科技有限责任公司 | Method for preparing high-carbon aldehyde |
| CN112225654A (en) * | 2020-11-02 | 2021-01-15 | 中国海洋石油集团有限公司 | Device and method for comprehensively utilizing mixed C4 |
| CN114621067A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | High-value utilization method of carbon-tetracarbon |
| CN115141090A (en) * | 2021-03-29 | 2022-10-04 | 中国石油化工股份有限公司 | Preparation method of olefine aldehyde |
| CN115141090B (en) * | 2021-03-29 | 2024-05-17 | 中国石油化工股份有限公司 | Preparation method of enal |
| CN113121614A (en) * | 2021-04-22 | 2021-07-16 | 中国科学院上海高等研究院 | Water-soluble metal-based complex and preparation method and application thereof |
| CN113559932A (en) * | 2021-06-30 | 2021-10-29 | 中国成达工程有限公司 | Catalyst system for synthesizing butanedialdehyde from acrolein hydroformylation |
| CN113559932B (en) * | 2021-06-30 | 2023-08-29 | 中国成达工程有限公司 | Catalyst system for synthesizing glyoxal by hydroformylation of acrolein |
| CN113402552A (en) * | 2021-07-21 | 2021-09-17 | 成都欣华源科技有限责任公司 | Catalyst for preparing aldehyde compound by hydroformylation of vegetable oil and method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109456154A (en) | A method of fatty aldehyde is prepared by hydroformylation reaction | |
| CN107790188B (en) | Metal-phosphine-containing organic copolymer catalyst and preparation method and application thereof | |
| CN111348995B (en) | Method for preparing aldehyde by olefin hydroformylation | |
| CN102911021A (en) | Method for preparing aldehyde through linear chain olefin hydroformylation | |
| CN1032538C (en) | Sulfonated 2,2'-bis (diphenxlphosphinomethyl)-1,1'-binaphthaline and preparation of same | |
| CN102649715B (en) | Method for preparing aldehyde through olefin hydrogen formylation | |
| CN102056872B (en) | Method for separating 1-butene from C4-containing hydrocarbon streams by hydroformylation | |
| CN101722048B (en) | Catalyst for preparing aldehyde by two-phase catalytic hydrogen formylation reaction and application thereof | |
| CN112794796B (en) | Method for preparing isononyl aldehyde by diisobutylene hydroformylation | |
| JP2017523127A (en) | Process for preparing unsaturated carboxylates | |
| CN110981709B (en) | Method for preparing aldehyde by hydroformylation of internal olefin | |
| CN107580593A (en) | The method for preparing salt unsaturated carboxylic acid | |
| CN106083551A (en) | A kind of hydroformylation of propene prepares the method for butyraldehyde | |
| CN106008184A (en) | Method for preparing 3-methyl butyraldehyde from isobutylene | |
| CN101522598B (en) | Process for coproduction of normal butanol and isobutyraldehyde | |
| CN112898140A (en) | Method for preparing aldehyde based on internal olefin catalyzed by phosphoramidite phosphine ligand | |
| CN1106374A (en) | Acidification of 1,3-butadiene | |
| CN106608816A (en) | Method for preparing C4-C8 aldehydes | |
| CN1202064C (en) | Process for preparing propionaldehyde from ethylene | |
| CN1171981A (en) | Catalyst ststems based on rhodium complexes containing diphosphine ligands and their use preparation of aldehydes | |
| CN100496736C (en) | Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation | |
| CN114849786B (en) | Imidazole sulfonic acid ionic liquid-based palladium phosphine complex catalyst for synthesizing methyl propionate through ethylene hydro-methyl esterification | |
| CN112679327B (en) | Method for preparing aldehyde compound by olefin two-phase hydroformylation | |
| CN112844488B (en) | Catalyst composition and application thereof in styrene hydroformylation reaction | |
| CN111470960B (en) | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190312 |
|
| RJ01 | Rejection of invention patent application after publication |