CN115322230A - Preparation method of oil-soluble rhodium-phosphine catalyst - Google Patents

Preparation method of oil-soluble rhodium-phosphine catalyst Download PDF

Info

Publication number
CN115322230A
CN115322230A CN202211161750.8A CN202211161750A CN115322230A CN 115322230 A CN115322230 A CN 115322230A CN 202211161750 A CN202211161750 A CN 202211161750A CN 115322230 A CN115322230 A CN 115322230A
Authority
CN
China
Prior art keywords
rhodium
acetylacetone
triphenylphosphine
stirring
trichloride
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
Application number
CN202211161750.8A
Other languages
Chinese (zh)
Inventor
张林燕
肖凤江
蒋璐璐
于尚燕
程仁鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Luxi Catalyst Co ltd
Original Assignee
Luxi Catalyst Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Luxi Catalyst Co ltd filed Critical Luxi Catalyst Co ltd
Priority to CN202211161750.8A priority Critical patent/CN115322230A/en
Publication of CN115322230A publication Critical patent/CN115322230A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of an oil-soluble rhodium-phosphine catalyst, which comprises the following steps: taking rhodium trichloride as a main raw material, reacting with acetylacetone and N, N-dimethylformamide to generate acetylacetone dicarbonyl rhodium, taking rhodium trichloride with the same mass, reacting with acetylacetone and N, N-dimethylformamide to generate acetylacetone dicarbonyl rhodium, then adding triphenylphosphine and sodium carbonate to react to generate di-triphenylphosphine carbonyl rhodium chloride, and mixing and reacting the acetylacetone dicarbonyl rhodium and the di-triphenylphosphine carbonyl rhodium chloride to obtain acetylacetone triphenylphosphine rhodium carbonyl; in the method, the principle of interconversion of intermediates is adopted, acetylacetonatocarbonyltriphenylphosphine rhodium is directly synthesized in three steps, and the preparation process is greatly reducedThe waste water yield can also effectively utilize the noble metal rhodium, the yield of the rhodium is improved, and the loss of the noble metal rhodium is effectively reduced.
Figure 100004_DEST_PATH_IMAGE002
Figure 100004_DEST_PATH_IMAGE003
Figure 100004_DEST_PATH_IMAGE004

Description

Preparation method of oil-soluble rhodium-phosphine catalyst
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of an oil-soluble rhodium-phosphine catalyst.
Background
The hydroformylation of olefins is a homogeneous catalytic reaction process in which olefins and synthesis gas are reacted to form aldehydes over transition metal complex catalysts, and is one of the most classical and important homogeneous organometallic catalyzed reactions. The basic reaction is to add a hydrogen atom and a formyl group to a double bond of an olefin (mainly, a terminal olefin). The hydroformylation reaction is a strongly exothermic reaction with a heat of reaction of about 125 kJ/mol. For an asymmetric olefin product, there are 2 possible configurations of the product aldehyde, normal and isomeric, due to the difference in the direction of double bond addition between (H) and (HCO). The normal aldehyde is usually a commercial product, so the normal/isomerization ratio is an important index for industrial production.
The catalyst has core importance on the hydroformylation reaction effect of the olefin, and has key influence on yield, reaction rate, energy consumption, chemoselectivity, regioselectivity and even stereoselectivity, so the research on the hydroformylation reaction of the olefin focuses on the development and improvement of the catalyst for many years.
The patent CN110938098A provides a preparation method of rhodium complex acetylacetone triphenylphosphine carbonyl rhodium, which comprises the steps of filling self-made redox resin into a reactor, adding a rhodium trichloride solution and a mixed solution of acetylacetone and triphenylphosphine into the reactor at a proper speed according to a proper proportion, and obtaining the rhodium complex acetylacetone triphenylphosphine carbonyl rhodium after the reaction is finished. Although the method realizes the continuity of the production process of the preparation method and shortens the production time, the yield is low and the noble metal rhodium cannot be fully utilized.
The invention solves the technical problems that the price of rhodium is extremely expensive and the production yield of acetylacetonatocarbonyltriphenylphosphine rhodium is generally low at present.
Disclosure of Invention
The invention provides a preparation method of an oil-soluble rhodium-phosphine catalyst, which is simple, convenient, high in yield and easy to operate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an oil-soluble rhodium-phosphine catalyst comprises the following steps: taking rhodium trichloride as a main raw material, reacting with acetylacetone and N, N-dimethylformamide to generate acetylacetone dicarbonyl rhodium, taking rhodium trichloride with the same mass, reacting with acetylacetone and N, N-dimethylformamide to generate acetylacetone dicarbonyl rhodium, then adding triphenylphosphine and sodium carbonate to react to generate di-triphenylphosphine carbonyl rhodium chloride, and mixing and reacting the acetylacetone dicarbonyl rhodium and the di-triphenylphosphine carbonyl rhodium chloride to obtain acetylacetone triphenylphosphine rhodium carbonyl;
Figure DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE003
Figure DEST_PATH_IMAGE004
。
the preparation method comprises the following steps:
(1) Adding N, N-dimethylformamide into rhodium trichloride, stirring to fully dissolve the rhodium trichloride, starting cooling and refluxing, heating to 100-170 ℃, adding acetylacetone to completely react, preserving heat for 1-4h, and then starting cooling to obtain an acetylacetone dicarbonyl rhodium solution;
(2) Adding N, N-dimethylformamide into rhodium trichloride, stirring to fully dissolve the rhodium trichloride, starting cooling and refluxing, heating to 100-170 ℃, adding acetylacetone to completely react, preserving heat for 1-4h, and then starting cooling to obtain an acetylacetone dicarbonyl rhodium solution;
(3) Adding a solvent into the acetylacetonatodicarbonylrhodium solution obtained in the step (1), adding water, and stirring for 2-15min;
(4) Adding triphenylphosphine and a solvent into a beaker, and stirring to completely dissolve the triphenylphosphine and the solvent; adding sodium carbonate and water into another beaker, and stirring to completely dissolve the sodium carbonate and the water;
(5) Adding the triphenylphosphine solution and the sodium carbonate solution prepared in the step (4) into the acetylacetonatodicarbonylrhodium solution obtained in the step (3) after stirring, and reacting for 10-60min to obtain di-triphenylphosphine carbonyl rhodium chloride;
(6) Mixing the acetylacetonatodicarbonylrhodium solution obtained in the step (2) with the bis-triphenylphosphine carbonyl rhodium chloride solution obtained in the step (5), starting stirring, and reacting at normal temperature for 0.5-4h;
(7) And (4) after the reaction is finished, carrying out rotary evaporation, centrifugation and washing on the solution obtained in the step (6) to obtain acetylacetonatocarbonyltriphenylphosphine rhodium.
Further, the method in the step (1) is the same as that in the step (2), and the mass ratio of the rhodium trichloride to the N, N-dimethylformamide to the acetylacetone is 1: 0.5-10.
Further, in the step (3), the solvent is toluene, dichloromethane or diethyl ether; the mass ratio of rhodium trichloride to solvent and water is as follows: 1:50-400:0.5-10.
Further, in the step (4), the solvent is toluene, dichloromethane or diethyl ether; the mass ratio of rhodium trichloride to triphenylphosphine to the solvent to sodium carbonate to water is as follows: 1:0.1-2:1-5:0.1-2:1-10.
The invention has the beneficial effects that:
the preparation technology provided by the invention utilizes the principle of interconversion of intermediates in the preparation process of the catalyst to directly synthesize the acetylacetone triphenylphosphine carbonyl rhodium in three steps, thereby not only greatly reducing the generation amount of wastewater in the preparation process, but also effectively utilizing the noble metal rhodium, improving the yield of the rhodium and effectively reducing the loss of the noble metal rhodium.
Drawings
FIG. 1 shows the spectrum of triphenylphosphine carbonyl rhodium acetylacetonate.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above objects, features and advantages of the present invention more comprehensible, the present invention is described in further detail with reference to examples.
Example 1
(1) Taking 20 g of rhodium chloride (the rhodium content is 38%), adding 100 g of N, N-dimethylformamide, stirring to fully dissolve the rhodium chloride, starting cooling and refluxing, heating to 120 ℃, adding 20 g of acetylacetone to completely react, preserving heat for 2 h, and then starting cooling to obtain acetylacetone dicarbonyl rhodium.
(2) Taking 20 g of rhodium chloride (the rhodium content is 38%), adding 100 g of N, N-dimethylformamide, stirring to fully dissolve the rhodium chloride, starting cooling and refluxing, heating to 120 ℃, adding 20 g of acetylacetone to completely react, preserving heat for 2 h, and then starting cooling to obtain acetylacetone dicarbonyl rhodium. 100 g of methylene chloride and 20 g of water were added to the resulting acetylacetonatodicarbonylrhodium solution, and the mixture was stirred for 10 minutes. 20 g of triphenylphosphine and 40 g of methylene chloride were added to the beaker, and the mixture was stirred to dissolve completely. To another beaker were added 10 g of sodium carbonate and 40 g of water, and the mixture was stirred to dissolve it completely. And adding the prepared triphenylphosphine solution and sodium carbonate solution into the acetylacetonatodicarbonylrhodium solution which is stirred, and reacting for 60min to obtain the di-triphenylphosphine carbonyl rhodium chloride.
(3) Mixing the obtained acetylacetonatodicarbonylrhodium solution with bis-triphenylphosphine carbonyl rhodium chloride solution, starting stirring, and reacting for 2 h. After the reaction is finished, the dichloromethane is completely evaporated from the obtained solid-liquid mixture by using a rotary evaporator at the temperature of 15 ℃. Finally, the solid-liquid mixture is centrifugally filtered and washed by ether and water respectively to obtain 70.5 g of acetylacetonatocarbonyltriphenylphosphine rhodium, the rhodium content is 20.8 percent, and the rhodium yield is 96.01 percent.
Example 2
(1) Taking 20 g of rhodium chloride (the rhodium content is 38%), adding 100 g of N, N-dimethylformamide, stirring to fully dissolve the rhodium chloride, starting cooling and refluxing, heating to 140 ℃, adding 20 g of acetylacetone to completely react, preserving heat for 2 h, and then starting cooling to obtain acetylacetone dicarbonyl rhodium.
(2) Taking 20 g of rhodium chloride (the rhodium content is 38%), adding 100 g of N, N-dimethylformamide, stirring to fully dissolve the rhodium chloride, starting cooling and refluxing, heating to 140 ℃, adding 20 g of acetylacetone to completely react, preserving heat for 2 h, and then starting cooling to obtain acetylacetone dicarbonyl rhodium. 100 g of methylene chloride and 20 g of water were added to the resulting acetylacetonatodicarbonylrhodium solution, and the mixture was stirred for 10 minutes. 20 g of triphenylphosphine and 40 g of methylene chloride were added to the beaker, and the mixture was stirred to dissolve completely. To another beaker were added 10 g of sodium carbonate and 40 g of water, and the mixture was stirred to dissolve it completely. And adding the prepared triphenylphosphine solution and sodium carbonate solution into the acetylacetonatodicarbonylrhodium solution which is stirred, and reacting for 60min to obtain the di-triphenylphosphine carbonyl rhodium chloride.
(3) Mixing the obtained acetylacetonatodicarbonylrhodium solution with bis-triphenylphosphine carbonyl rhodium chloride solution, starting stirring, and reacting for 2 h. After the reaction is finished, the dichloromethane is completely evaporated from the obtained solid-liquid mixture by using a rotary evaporator at the temperature of 15 ℃. Finally, the solid-liquid mixture was subjected to centrifugal filtration and washed with diethyl ether and water, respectively, to obtain 68.3 g of acetylacetonatotriphenylphosphine carbonylrhodium, the rhodium content was 20.8%, and the rhodium yield was 93.01%.
Comparative example 1
(1) Taking 20 g of rhodium chloride (the rhodium content is 38%), adding 100 g of N, N-dimethylformamide, stirring to fully dissolve the rhodium chloride, starting cooling and refluxing, heating to 120 ℃, adding 20 g of acetylacetone to completely react, preserving heat for 2 h, and then starting cooling to obtain acetylacetone dicarbonyl rhodium.
(2) Taking 20 g of rhodium chloride (the rhodium content is 38%), adding 100 g of N, N-dimethylformamide, stirring to fully dissolve the rhodium chloride, starting cooling and refluxing, adding 20 g of acetylacetone when the temperature is raised to 120 ℃ to completely react, preserving the temperature for 2 hours, and then starting cooling to obtain acetylacetone dicarbonyl rhodium. To the resulting rhodium acetylacetonate dicarbonyl solution, 100 g of methylene chloride and 20 g of water were added and the mixture was stirred for 10 minutes. 20 g of triphenylphosphine and 40 g of methylene chloride were added to the beaker, and the mixture was stirred to dissolve completely. 20 g of sodium carbonate and 80 g of water were added to another beaker and stirred to dissolve them completely. And adding the prepared triphenylphosphine solution and sodium carbonate solution into the acetylacetonatodicarbonylrhodium solution which is stirred, and reacting for 60min to obtain the di-triphenylphosphine carbonyl rhodium chloride.
(3) Mixing the obtained acetylacetonatodicarbonylrhodium solution with bis-triphenylphosphine carbonyl rhodium chloride solution, starting stirring, and reacting for 2 h. After the reaction is finished, the dichloromethane is completely evaporated from the obtained solid-liquid mixture by using a rotary evaporator at the temperature of 15 ℃. Finally, the solid-liquid mixture was subjected to centrifugal filtration and washed with diethyl ether and water, respectively, to obtain 65.8 g of acetylacetonatotriphenylphosphine carbonylrhodium, the rhodium content was 20.8%, and the rhodium yield was 89.61%.
Comparative example 2
(1) Taking 20 g of rhodium chloride (the rhodium content is 38%), adding 100 g of N, N-dimethylformamide, stirring to fully dissolve the rhodium chloride, starting cooling and refluxing, heating to 120 ℃, adding 20 g of acetylacetone to completely react, preserving heat for 2 h, and then starting cooling to obtain acetylacetone dicarbonyl rhodium.
(2) Taking 20 g of rhodium chloride (the rhodium content is 38%), adding 100 g of N, N-dimethylformamide, stirring to fully dissolve the rhodium chloride, starting cooling and refluxing, heating to 120 ℃, adding 20 g of acetylacetone to completely react, preserving heat for 2 h, and then starting cooling to obtain acetylacetone dicarbonyl rhodium. To the resulting rhodium acetylacetonate dicarbonyl solution, 100 g of methylene chloride and 20 g of water were added and the mixture was stirred for 10 minutes. 10 g of triphenylphosphine and 20 g of methylene chloride were added to the beaker, and the mixture was stirred to dissolve completely. To another beaker was added 20 g of sodium carbonate and 80 g of water, and stirred to dissolve it completely. And adding the prepared triphenylphosphine solution and sodium carbonate solution into the acetylacetonatodicarbonylrhodium solution which is stirred, and reacting for 60min to obtain the di-triphenylphosphine carbonyl rhodium chloride.
(3) Mixing the obtained acetylacetonatodicarbonylrhodium solution with bis-triphenylphosphine carbonyl rhodium chloride solution, starting stirring, and reacting for 2 h. After the reaction was completed, the obtained solid-liquid mixture was completely evaporated with dichloromethane by using a rotary evaporator at 15 ℃. Finally, the solid-liquid mixture was subjected to centrifugal filtration and washed with diethyl ether and water, respectively, to obtain 61.2 g of acetylacetonatotriphenylphosphine carbonylrhodium, the rhodium content was 20.8%, and the rhodium yield was 83.34%.

Claims (5)

1. A preparation method of an oil-soluble rhodium-phosphine catalyst is characterized by comprising the following steps: taking rhodium trichloride as a main raw material, reacting with acetylacetone and N, N-dimethylformamide to generate acetylacetone dicarbonyl rhodium, taking rhodium trichloride with the same mass, reacting with acetylacetone and N, N-dimethylformamide to generate acetylacetone dicarbonyl rhodium, then adding triphenylphosphine and sodium carbonate to react to generate di-triphenylphosphine carbonyl rhodium chloride, and mixing the acetylacetone dicarbonyl rhodium and the di-triphenylphosphine carbonyl rhodium chloride to react to obtain acetylacetone triphenylphosphine rhodium carbonyl.
2. The preparation method of the oil-soluble rhodium-phosphine catalyst according to claim 1, which is characterized by comprising the following steps:
(1) Adding N, N-dimethylformamide into rhodium trichloride, stirring to fully dissolve the rhodium trichloride, starting cooling and refluxing, heating to 100-170 ℃, adding acetylacetone to completely react, preserving heat for 1-4h, and then starting cooling to obtain an acetylacetone dicarbonyl rhodium solution;
(2) Adding N, N-dimethylformamide into rhodium trichloride, stirring to fully dissolve the rhodium trichloride, starting cooling and refluxing, adding acetylacetone when the temperature is raised to 100-170 ℃ to completely react, and keeping the temperature for 1-4h and then starting cooling to obtain an acetylacetone dicarbonyl rhodium solution;
(3) Adding a solvent into the acetylacetonatodicarbonyl rhodium solution obtained in the step (1), adding water, and stirring for 2-15min;
(4) Adding triphenylphosphine and a solvent into a beaker, and stirring to completely dissolve the triphenylphosphine and the solvent; adding sodium carbonate and water into another beaker, and stirring to completely dissolve the sodium carbonate and the water;
(5) Adding the triphenylphosphine solution and the sodium carbonate solution prepared in the step (4) into the acetylacetonatodicarbonylrhodium solution obtained in the step (3) after stirring, and reacting for 10-60min to obtain di-triphenylphosphine carbonyl rhodium chloride;
(6) Mixing the acetylacetonatodicarbonylrhodium solution obtained in the step (2) with the bis-triphenylphosphine carbonyl rhodium chloride solution obtained in the step (5), starting stirring, and reacting at normal temperature for 0.5-4h;
(7) And (4) after the reaction is finished, carrying out rotary evaporation, centrifugation and washing on the solution obtained in the step (6) to obtain acetylacetonatocarbonyltriphenylphosphine rhodium.
3. The method for preparing the oil-soluble rhodium-phosphine catalyst according to claim 2, wherein the method in the step (1) is the same as that in the step (2), and the mass ratio of the rhodium trichloride to the N, N-dimethylformamide to the acetylacetone is 1: 0.5-10.
4. The method for preparing an oil soluble rhodium phosphine catalyst according to claim 2, wherein the solvent in the step (3) is toluene, dichloromethane or diethyl ether; the mass ratio of rhodium trichloride to solvent and water is as follows: 1:50-400:0.5-10.
5. The process of claim 2, wherein the solvent in step (4) is toluene, dichloromethane or diethyl ether; the mass ratio of rhodium trichloride to triphenylphosphine to the solvent to sodium carbonate to water is as follows: 1:0.1-2:1-5:0.1-2:1-10.
CN202211161750.8A 2022-09-23 2022-09-23 Preparation method of oil-soluble rhodium-phosphine catalyst Pending CN115322230A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211161750.8A CN115322230A (en) 2022-09-23 2022-09-23 Preparation method of oil-soluble rhodium-phosphine catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211161750.8A CN115322230A (en) 2022-09-23 2022-09-23 Preparation method of oil-soluble rhodium-phosphine catalyst

Publications (1)

Publication Number Publication Date
CN115322230A true CN115322230A (en) 2022-11-11

Family

ID=83913346

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211161750.8A Pending CN115322230A (en) 2022-09-23 2022-09-23 Preparation method of oil-soluble rhodium-phosphine catalyst

Country Status (1)

Country Link
CN (1) CN115322230A (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107021983A (en) * 2017-04-12 2017-08-08 山东博苑医药化学有限公司 The resource recycling Application way of butyl octanol unit rhodium-containing waste liquid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107021983A (en) * 2017-04-12 2017-08-08 山东博苑医药化学有限公司 The resource recycling Application way of butyl octanol unit rhodium-containing waste liquid

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SI CHEN等: "Slow Exchange of Bidentate Ligands between Rhodium(I) Complexes: Evidence of Both Neutral and Anionic Ligand Exchange", 《EUR. J. INORG. CHEM》, pages 5820 *
余娟等: "两种乙酰丙酮·羰基铑化合物的合成与晶体结构表征", 《贵金属》, vol. 37, pages 8 - 25 *
王胜国等: "乙酰丙酮三苯基膦羰基铑( I )的合成与表征", 《贵金属》, vol. 26, pages 43 - 46 *

Similar Documents

Publication Publication Date Title
CN112500431B (en) Preparation method of olefin hydroformylation catalyst system
CN110105169B (en) Method for preparing 1, 3-propylene glycol by coupling ethylene oxide with synthesis gas
CN111039980B (en) Cuprous complex containing diphosphine o-carborane ligand and preparation and application thereof
CN103221368A (en) Conversion of alcohols
CN113492021B (en) Preparation method of rhodium catalyst
CN111097416A (en) Preparation of carbon-supported cobalt heterogeneous catalyst and application of carbon-supported cobalt heterogeneous catalyst in catalyzing hydroformylation reaction of olefin
CN106588619A (en) Method for preparing aldehyde through olefin hydroformylation
CN112742482A (en) Catalyst for catalytic hydrogenation, preparation method and application thereof
CN115672407A (en) Phosphine ligand modified carbon-supported monatomic rhodium catalyst and preparation and application methods thereof
CN103240123A (en) Method for preparing supported Schiff base metal complex catalyst
CN115322230A (en) Preparation method of oil-soluble rhodium-phosphine catalyst
CN110590837A (en) Synthesis method of bis (2-methoxyphenyl) phosphine oxide
CN114534795A (en) Catalyst for preparing valeraldehyde through butene hydroformylation, preparation method of catalyst and preparation method of valeraldehyde
CN109126879B (en) Nitrogen-phosphorus coordination metal catalyst and method for preparing 3-hydroxy propionate through catalysis
CN113083374A (en) Immobilized multi-tooth phosphine-rhodium complex catalyst and application thereof
CN101418014B (en) Method for preparing tetraphenyl phosphoric bromide
CN105541918B (en) A kind of chirality 5,5,10,10 4 aryl two ring [4.4.0] 3,8 bis phosphoric acid and its preparation method and application
WO2018163004A1 (en) Hydrogen production from ethylene glycol under basic conditions
CN114133412B (en) Preparation method of chiral 1, 2-bis [ (2-methoxyphenyl) phenylphosphinyl ] ethane
CN106674285A (en) Method for preparing acetylacetonatocarbonyltriphenylp hosphinerhodium
CN111039765A (en) Method for preparing 3-alkoxy propionaldehyde
CN115845927B (en) Cobalt complex catalyst for synthesizing carboxylic acid, preparation method and application thereof
CN113244957B (en) Polymeric carbene iridium catalyst and preparation method and application thereof
CN101293213B (en) Rhodium catalyst for carbonyl synthesis of acetic anhydride and preparation method thereof
CN115364903B (en) Preparation method of catalyst for synthesizing alpha-hydroxyketone

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