CN109821567A - A kind of heterogeneous Co base catalyst of olefin hydroformylation and preparation method thereof - Google Patents
A kind of heterogeneous Co base catalyst of olefin hydroformylation and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to heterogeneous Co base catalyst of a kind of olefin hydroformylation and preparation method thereof, it is intended to overcome the problems, such as that the isolation technics problem of homogeneous catalyst, the existing heterogeneous catalysis target product yield of solution are low.Co element is supported on the carrier with high-specific surface area and is modified by the present invention, and forming active component is M1xM2yCoAzThe base supported heterogeneous catalysis of Co, change Co atomic electrons state, its active site can be made evenly dispersed and its activity, and stability with higher in air.The method for preparing catalyst is simple, easy to maintain, the high income of obtained target product aldehyde.
Description
Technical field
The invention belongs to catalyst preparation technical field, be related to a kind of heterogeneous Co base catalyst of olefin hydroformylation and its
Preparation method.
Background technique
Hydroformylation of olefin product is the aldehyde or alcohol of a carbon more than raw material olefin, is a kind of important organic chemical industry
Raw material, the production for plasticizer, surfactant, additive, solvent, intermediate and fragrance etc..Hydroformylation of olefin
Homogeneous metal rhodium ligand catalyst is mainly used at present, and homogeneous catalyst has excellent catalytic activity, shows outstanding
Conversion ratio and selectivity, play an important role in industrial application.However, but there is catalysis in homogeneous catalysis hydroformylation reaction
The disadvantages of agent is at high cost, difficult separation and recycling and separation costs are high, this just largely limits its development, therefore in recent years
Research about homogeneous catalyst is concentrated mainly in the separation of catalyst.
The research and development of olefin hydroformylation heterogeneous catalysis become hot subject in recent years, are to solve homogeneous catalyst point
From difficult important channel.Xingang Li et al. (Journal of Membrane Science, 2010, volume 347,
220-227 pages) with Silicalite-1 encapsulate Rh/AC catalyst, utilize molecular sieve pore passage different permeabilities carry out 1- hexene
Hydroformylation reaction can significantly improve the selectivity of n-alkanal, just different than being increased to 3.2 by 0.6, but conversion ratio is by 98.5%
It is down to 18.3%.
Patent CN106861761A, CN108069842A, CN105749969B, which are disclosed, loads organic polymer containing phosphine
Hydroformylation heterogeneous catalysis on porous support, but such catalyst activity is catalyzed significantly lower than conventional homogeneous
Agent, and it is easy to fall off there are activated centre the problems such as.Patent CN107469815A, CN107999061A is disclosed nano metal rhodium
It is supported on different nano-tube materials, the method for obtaining a kind of efficient hydroformylation reaction heterogeneous catalysis will be active
Center nanometer Rh is dispersed on carrier, but noble metal Rh is expensive, and the preparation cost of such catalyst is higher.
The present invention chooses with high-specific surface area or has certain influence or with regular to active component electronic property
The carrier of the features such as cellular structure, the Co base active component of load height dispersion, by the other metals or non-gold of different proportion
Belong to element to the modulation of its electronic property, obtains the alkene that wide adaptation range, performance indicator are high and are easily isolated and recycle
Hydrocarbon heterogeneous catalysis.
Summary of the invention
It is an object of the present invention to provide heterogeneous Co base catalyst of a kind of olefin hydroformylation and preparation method thereof.
The separation of conventional homogeneous catalyst is difficult；Co base catalyst (such as Co-B, Co-P amorphous material) has alkene hydrogen
Formylation reaction activity, but it is easy crystallization in air and is easy to reunite, and product yield is not high；After Rh base catalyst is immobilized
Activity also declines to a great extent, and activated centre is easy to fall off.In order to overcome isolation technics problem, the solution of homogeneous catalyst existing non-
The low problem of homogeneous catalyst target product yield, the present invention propose a kind of heterogeneous Co base catalyst of olefin hydroformylation and its
Co element is supported on the carrier with high-specific surface area and is modified by preparation method, and forming active component is
M1xM2yCoAzThe base supported heterogeneous catalysis of Co, change Co atomic electrons state, its active site can be made uniformly to divide
It dissipates, and its activity can be improved, and stability with higher in air.The method for preparing catalyst is simple, easy to maintain, obtains
The high income of the target product aldehyde arrived.
The active component M1 that catalyst of the present invention contains metal M1, M2, nonmetallic ingredient A and Co are formedxM2yCoAz, x, y,
The range of z is respectively 0 ~ 5,0.01~10 and 1 ~ 10；There are high forces between M2 and Co, A；Catalyst active center is with Co
Main, catalyst structure is there are amorphous alloy form (mainly being formed between Co and element A) it has further been found that the catalyst obtained
Some will form solid solution structure, and element dispersion degree is equally relatively high, and activity is also relatively good；M1, M2 and element A all may be used
Adjust Co electronic property simultaneously play the role of high degree of dispersion, while these elements also have priming reaction substrate (alkene, CO and
H2) ability；Activation substrate ability, which is stablized, improves feed stock conversion, changes electronic property and improves catalyst hydrogen formyl
Change rate, high degree of dispersion makes catalyst have preferable catalyst life and intensity, and the interaction between element is so that this is urged
Agent preparation and preservation condition routinize, without harsh preparation and preservation condition, easily aoxidized unlike pure Co-B and
Inactivation.Catalyst contains support and improves the carrier of element dispersion degree；Carrier include SBA-15, MCM-41, ZSM-5,
Silicalite-1, carbon nanotube, active carbon, graphene；M2, Co, A are dispersed in carrier surface and duct in catalyst, are
Heterogeneous catalyst.
The present invention is with M1xM2yCoAzIt is prepared on the carriers such as load and the biggish molecular sieve of specific surface area, active carbon non-
Homogeneous catalyst on the basis of guaranteeing catalytic activity, while solving conventional homogeneous catalyst and being difficult to separate and recycle with product
The technical problem utilized.
The present invention prepares M1 using chemical reduction methodxM2yCoAzHeterogeneous catalyst, carrier SBA-15, MCM-
41, ZSM-5, Silicalite-1, carbon nanotube, active carbon, graphene etc..By improving in specific surface area of catalyst and activity
Heart dispersion degree controls activated centre chemical environment, improves absorption and the active rate of raw material, realizes the mesh for improving product yield
's.
The active component M1 that catalyst contains metal M1, M2, nonmetallic ingredient A and Co are formedxM2yCoAz, the model of x, y, z
Enclose respectively 0 ~ 5,0.01~10 and 1 ~ 10；Simultaneously containing the carrier for supporting and improving element dispersion degree；It is obtained heterogeneous
Catalyst has excellent hydroformylation activity and high positive Isomer ratio to alkene.
Active component is highly dispersed in carrier surface and duct in catalyst, is heterogeneous catalyst；Metal
There are certain interaction force, three's electronic property is substantially change by M2 and nonmetallic A and Co, while can play dispersion Co
High uniformity dispersity is presented in the effect of atom, i.e. three kinds of elements, is dispersed by atomic level or is dispersed in the form of nanocluster,
Metal M1 provides certain alkalinity or electrical adjustment effect.
The preparation method of catalyst includes following key step:
(1) soluble salt solution for preparing a certain concentration metal M2 component, is denoted as solution B；
(2) HCI solution for preparing a certain concentration metal M1 component, is denoted as solution C；
(3) soluble salt solutions of the desired amount of cobalt newly matched are added in solution B, dissolution is sufficiently stirred, obtains solution D；
(4) solution C is added in solution D, mixing is sufficiently stirred, obtains solution E；
(3) it weighs the desired amount of carrier to be added in solution E, stir for 24 hours, wherein 2~6h of ultrasonic treatment obtains suspension F；
(4) 80~90 DEG C of dry suspension F, 80 DEG C of dry 10h obtain powder G in vacuum oven；
(5) by powder G in nitrogen atmosphere 350 DEG C~550 DEG C 2~6h of calcination process, obtain powder H；
(6) powder H is transferred in three-necked flask, deionized water is added, is stirred evenly under ice-water bath, leads to nitrogen protection, obtains
Suspension I；
(7) inorganic salts or oxysalt solution J of nonmetallic A are prepared, wherein cation is preferably metal component M1；If solution
J is free of metal M1 component, then individually adds the hydrochloric acid or nitric acid solution of M1, forms solution J；
(8) the desired amount of solution J is measured, is added dropwise in suspension I, reacts 0.5h after being added dropwise to complete again, obtain suspension K；
(9) suspension K is washed to neutrality, then is respectively washed 3 times with dehydrated alcohol and toluene, obtained powder drying and in nitrogen
High-temperature roasting under gas or argon atmosphere；
(10) if Co element has been reduced in step (8), then (9) step obtains the heterogeneous Co base of olefin hydroformylation and urges
Agent；If reduction reaction could not occur, then material synthesis gas, H should be used before the use2Or one of CO is gone back again
It is former.
Technical solution of the present invention further includes following characteristics:
(1) valence stability between catalyst elements, interation between nutrients inhibit oxidation.
(2) catalyst is applied to slurry bed system, also can be directly used for other suitable reactors such as fixed bed, utilizes catalyst
Middle metallic element characteristic is easy to realize being separated by filtration or Magnetic Isolation and recycling for solid-liquid with product.
(3) catalyst is applied in hydroformylation of olefin, and alpha-olefin, internal olefin etc. are in M1xM2yCoAzEffect is lower to be added
Corresponding aldehyde is made in hydrogen, when being applied to alpha hydroformylation of olefin, can significantly improve just different ratio.
(4) active component of catalyst is dispersed in carrier hole or (is such as passed through altogether with surface by certain effect
Hydroxyl effect in the form and carrier of valence link etc.) it combines, high-temperature roasting back loading is relatively secured, and catalyst Yi Yushi
It is now separated by solid-liquid separation and is recycled.
(5) range of x, y, z is respectively 0 ~ 5,0.01~10 and 1 ~ 10.
(6) in method for preparing catalyst, the soluble-salt of M2 and the soluble-salt additive amount of cobalt, with M2:Co mol ratio
Meter is 0.01~1:1.
(7) catalyst is supported on high-specific surface area or has certain influence or with rule to active component electronic property
The carrier surface of whole cellular structure.
(8) catalyst carrier specific surface area is greater than 550m2/ g, aperture is in 5~20nm, the preferably carrier of 7-8nm.
(9) calcination process of preparation step (5) is temperature-gradient method processing, is warming up to 200 from room temperature with the rate of 2 DEG C/min
DEG C, then 350 DEG C are warming up to the rate of 2 DEG C/min, 5h is roasted, wherein N2Flow velocity is 50~150mL/min.
(10) catalyst metals element dispersion degree reaches 0.8 or more.
The alkene is a kind of monoolefine or mixed olefins, and carbon number is preferably 6 ~ 12, and normal olefine and isomeric olefine all may be used
With, preferred normal olefine, especially positive structure linear alpha-olefin.The metal M1 be one of IA and Group IIA element or a variety of, it is excellent
It is selected as the one or more of Na, K, Mg, Ca and Sr；The metal M2 be mainly transition metal element or major element Ga, In,
One of Sn, Sb and Bi or a variety of；The transition metal element include Cr, Mn, Fe, Ni, Cu, Zn, Mo, W, Ru, Rh, Pd,
Pt, Au and Ag.Preferably one of Ni, Fe, Rh and Sn or a variety of.The nonmetallic A includes the one of P, B, N, Se, Te, F, C
Kind or a variety of, preferably P or B.The carrier includes SBA-15, MCM-41, ZSM-5, Silicalite-1, carbon nanotube, work
Property charcoal, mesoporous aluminas, graphene etc. it is one or more, be characterized in high-specific surface area or electro to active component
Matter has certain influence or with regular cellular structure, meets one or more of them feature；
Some will form solid solution structure with the catalyst obtained in the present invention, and element dispersion degree is equally relatively high, activity
Also relatively good, from another aspect provides a kind of immobilized methods of olefin hydroformylation catalyst, by M2, Co and other elements
Metal is formed, to be fixed on porous carrier surface, carried catalyst is similar with immobilized preceding homogeneous catalyst performance, active group
Divide in single reaction and is not lost substantially.
The present invention, for carrier, is verified with the active carbon of high-specific surface area, MCM41, SBA-15 etc. with reliable experimental data
M1xM2yCoAzWith high hydroformylation reaction activity under carrier collective effect, has been reached, conversion ratio reaches 99%, and metal is not
It is easy to run off.Catalyst life shows that the catalyst shows good recycling performance in 300h or more verifying.
The determination of activity step of catalyst of the present invention: carrying out in interval paste state bed reactor, and unstripped gas group becomes CO:H2
=1:1, solvent medium toluene 7.5mL, raw material olefin 2.5mL, catalyst 0.125g, 120 DEG C of reaction temperature, reaction pressure 5MPa,
Mixing speed 1200r.p.m, reaction time 4h.
Detailed description of the invention
Fig. 1 is the wide-angle XRD object phasor of 1 catalyst sample of embodiment.
Fig. 2 is the small angle XRD object phasor of 1 catalyst sample of embodiment.
Specific embodiment
Below by embodiment, the present invention is further elaborated, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
Prepare the cobalt chloride solution of 0.1mol/L.Weigh the NiCl of 1.6g2﹒ 6H2O, the cobalt chloride for being dissolved in 68mL0.1mol/L are molten
2g carrier S BA-15 is added in liquid, stirs for 24 hours, wherein ultrasound 2h.It is evaporated in blender, the dry 10h of 80 DEG C of vacuum ovens；
In nitrogen atmosphere, obtained powder is transferred in three-necked flask by 350 DEG C of calcination process 5h, and 68mL deionized water, N is added2Atmosphere
It encloses and is stirred evenly under lower ice-water bath, prepare 0.1mol/L sodium borohydride solution, measure the 28mL solution and be added dropwise to three necks burning
In bottle, 0.5h is reacted after being added dropwise to complete again；Gained suspension is washed to neutrality and is used further to water-ethanol washing 3 times, needed for obtaining
Catalyst n a-Ni-Co-B/SBA-15.The evaluation of 1- hexene hydroformylation activity: unstripped gas forms CO:H2=1:1, reaction temperature
It is 120oC, revolving speed are 1200 r.p.m, and reaction pressure 5MPa, reaction time 4h the results are shown in Table 1.
Embodiment 2
Prepare the cobalt chloride solution of 0.1mol/L.Weigh the FeCl of 0.8g3﹒ 6H2O, the cobalt chloride for being dissolved in 68mL0.1mol/L are molten
2g carrier MCM-41 is added in liquid, stirs for 24 hours, wherein ultrasound 2h.It is evaporated in blender, the dry 10h of 80 DEG C of vacuum ovens；
In nitrogen atmosphere, obtained powder is transferred in three-necked flask by 350 DEG C of calcination process 5h, and 68mL deionized water, N is added2Atmosphere
It encloses and is stirred evenly under lower ice-water bath, prepare 0.1mol/L solution of potassium borohydride, measure the 24mL solution and be added dropwise to three necks burning
In bottle, 0.5h is reacted after being added dropwise to complete again；Gained suspension is washed to neutrality and is used further to water-ethanol washing 3 times, needed for obtaining
Catalyst K-Fe-Co-B/MCM-41.The evaluation of 1- octene hydroformylation activity: unstripped gas forms H2: CO=1:1, reaction temperature
It is 120oC, revolving speed are 1200 r.p.m, and reaction pressure 5MPa, reaction time 4h the results are shown in Table 1.
Embodiment 3
Prepare the cobalt chloride solution of 0.1mol/L.Weigh the RhCl of 0.5g2﹒ 6H2O, the cobalt chloride for being dissolved in 68mL0.1mol/L are molten
2g carrier ZSM-5 is added in liquid, stirs for 24 hours, wherein ultrasound 2h.It is evaporated in blender, the dry 10h of 80 DEG C of vacuum ovens；Nitrogen
During atmosphere is enclosed, obtained powder is transferred in three-necked flask by 350 DEG C of calcination process 5h, and 68mL deionized water, N is added2Atmosphere
It is stirred evenly under lower ice-water bath, prepares 0.1mol/L calcium borohydride solution, measured the 20mL solution and be added dropwise to three-neck flask
In, 0.5h is reacted after being added dropwise to complete again；Gained suspension is washed to neutrality and is used further to water-ethanol washing 3 times, is urged needed for obtaining
Agent Ca-Rh-Co-B/ZSM-5.The evaluation of 1- octene hydroformylation activity: unstripped gas forms H2: CO=1:1, reaction temperature are
120oC, revolving speed are 1200 r.p.m, and reaction pressure 5MPa, reaction time 4h the results are shown in Table 1.
Embodiment 4
Prepare the cobalt chloride solution of 0.1mol/L.Weigh the SnCl of 0.2g2﹒ 6H2O, the cobalt chloride for being dissolved in 68mL0.1mol/L are molten
2g carrier graphene is added in liquid, stirs for 24 hours, wherein ultrasound 2h.It is evaporated in blender, the dry 10h of 80 DEG C of vacuum ovens；
In nitrogen atmosphere, obtained powder is transferred in three-necked flask by 350 DEG C of calcination process 5h, and 68mL deionized water, N is added2Atmosphere
It encloses and is stirred evenly under lower ice-water bath, prepare 0.1mol/L hydrogen phosphite sodium solution, measure the 17mL solution and be added dropwise to three necks
In flask, 0.5h is reacted after being added dropwise to complete again；Gained suspension is washed to neutrality and is used further to water-ethanol washing 3 times, obtains institute
Need catalyst n a-Sn-Co-P/ graphene.The evaluation of 1- decene hydroformylation activity: unstripped gas forms H2: CO=1:1, reaction temperature
Degree is 120oC, revolving speed are 1200 r.p.m, and reaction pressure 5MPa, reaction time 4h the results are shown in Table 1.
Embodiment 5
Prepare the cobalt chloride solution of 0.1mol/L.Weigh the ZnCl of 0.1g2﹒ 6H2O, the cobalt chloride for being dissolved in 68mL0.1mol/L are molten
2g carrier S BA-15 is added in liquid, stirs for 24 hours, wherein ultrasound 2h.It is evaporated in blender, the dry 10h of 80 DEG C of vacuum ovens；
In nitrogen atmosphere, obtained powder is transferred in three-necked flask by 350 DEG C of calcination process 5h, and 68mL deionized water, N is added2Atmosphere
It encloses and is stirred evenly under lower ice-water bath, prepare 0.1mol/L sodium borohydride solution, measure the 14mL solution and be added dropwise to three necks burning
In bottle, 0.5h is reacted after being added dropwise to complete again；Gained suspension is washed to neutrality and is used further to water-ethanol washing 3 times, needed for obtaining
Catalyst n a-Zn-Co-B/SBA-15.The evaluation of styrene hydroformylation activity: unstripped gas forms H2: CO=1:1, reaction temperature
It is 120oC, revolving speed are 1200 r.p.m, and reaction pressure 5MPa, reaction time 4h the results are shown in Table 1.
Embodiment 6
Prepare the cobalt chloride solution of 0.1mol/L.Weigh the NiCl of 0.1g2﹒ 6H2O, the cobalt chloride for being dissolved in 68mL0.1mol/L are molten
2g carrier mesoporous aluminas is added in liquid, stirs for 24 hours, wherein ultrasound 2h.It is evaporated in blender, 80 DEG C of vacuum ovens are dry
10h；In nitrogen atmosphere, obtained powder is transferred in three-necked flask by 350 DEG C of calcination process 5h, and 68mL deionized water is added,
N2It is stirred evenly under ice-water bath under atmosphere, prepares 0.1mol/L magnesium borohydride solution, measured the 28mL solution and be added dropwise to three
In neck flask, 0.5h is reacted after being added dropwise to complete again；Gained suspension is washed to neutrality and is used further to water-ethanol washing 3 times, is obtained
Required catalyst Mg-Ni-Co-B/ mesoporous aluminas.The evaluation of 1- decene hydroformylation activity: unstripped gas forms H2: CO=1:1,
Reaction temperature is 120oC, revolving speed are 1200 r.p.m, and reaction pressure 5MPa, reaction time 4h the results are shown in Table 1.Table 1 is catalysis
The hydroformylation of olefin activity of agent.
Embodiment 7
Catalyst preparation is referring to embodiment 2.
Hydroformylation reaction activity rating: referring to embodiment 1, reaction temperature is 130 DEG C, the results are shown in Table one.
Embodiment 8
Catalyst preparation is referring to embodiment 2: carrier is active carbon.
Hydroformylation reaction activity rating: referring to embodiment 1, reaction temperature is 130 DEG C, the results are shown in Table one.
Embodiment 9
Catalyst preparation is referring to embodiment 2, carrier MCM-41.
Hydroformylation reaction activity rating: referring to embodiment 1, reaction pressure 7MPa the results are shown in Table one.
Embodiment 10
Catalyst preparation is referring to embodiment 2, carrier Silicalite-1.
Hydroformylation reaction activity rating: referring to embodiment 1, reaction pressure 9MPa the results are shown in Table 1.
For Fig. 1 and Fig. 2 it is found that 1 wide-angle XRD diagram of embodiment, catalyst have the last one disperse peak at 2 θ=23 °, this is carrier
The disperse peak that silica generates in SBA-15.Occurs a weak widthization disperse peak at 47 ° of 2 θ ≈, this belongs to Ni-B, Co-
B amorphous structure.Fig. 2 is small angle XRD diagram, corresponding (100) crystal face of strong diffraction maximum of the catalyst near 2 θ=0.86 °, 1.46 °
Two weaker diffraction maximums with 1.68 ° respectively correspond (110) and (200) crystal face of SBA-15, illustrate Ni-Co-B amorphous alloy
Uniform load is in carrier surface and the skeleton structure without destroying SBA-15.
The hydroformylation of olefin activity of 1 catalyst of table
| Embodiment | Conversion ratio/% | Enanthaldehyde yield/% |
| 1 | 92.2 | 74.5 |
| 2 | 75.0 | 62.3 |
| 3 | 79.1 | 60.3 |
| 4 | 88.6 | 72.2 |
| 5 | 76.7 | 65.3 |
| 6 | 83.6 | 82.4 |
| 7 | 98.6 | 86.4 |
| 8 | 92.3 | 74.4 |
| 9 | 96.8 | 82.6 |
| 10 | 98.2 | 85.2 |
Claims (4)
1. a kind of heterogeneous Co base catalyst of olefin hydroformylation and preparation method thereof, it is characterised in that:
The active component M1 that the catalyst contains metal M1, M2, nonmetallic ingredient A and Co are formedxM2yCoAz, the model of x, y, z
Enclose respectively 0 ~ 5,0.01~10 and 1 ~ 10；Simultaneously containing the carrier for supporting and improving element dispersion degree；It is obtained heterogeneous
Catalyst has excellent hydroformylation activity and high positive Isomer ratio to alkene；
It is characterized in that active component is highly dispersed in carrier surface and duct in catalyst, it is support type heterogeneous catalysis
Agent；There are certain interaction force, three's electronic property is substantially change, while can be risen by metal M2 and nonmetallic A and Co
To the effect of dispersion Co atom, i.e. three kinds of elements are presented high uniformity dispersity, are dispersed with atomic level or with nanocluster
Form dispersion, metal M1 provide certain alkalinity or electrical adjustment effect；
The preparation method of the catalyst includes following key step:
(1) soluble salt solution for preparing a certain concentration metal M2 component, is denoted as solution B；
(2) HCI solution for preparing a certain concentration metal M1 component, is denoted as solution C；
(3) soluble salt solutions of the desired amount of cobalt newly matched are added in solution B, dissolution is sufficiently stirred, obtains solution D；
(4) solution C is added in solution D, mixing is sufficiently stirred, obtains solution E；
(3) it weighs the desired amount of carrier to be added in solution E, stir for 24 hours, wherein 2~6h of ultrasonic treatment obtains suspension F；
(4) 80~90 DEG C of dry suspension F, 80 DEG C of dry 10h obtain powder G in vacuum oven；
(5) by powder G in nitrogen atmosphere 350 DEG C~550 DEG C 2~6h of calcination process, obtain powder H；
(6) powder H is transferred in three-necked flask, deionized water is added, is stirred evenly under ice-water bath, leads to nitrogen protection, obtains
Suspension I；
(7) inorganic salts or oxysalt solution J of nonmetallic A are prepared, wherein cation is preferably metal component M1；If solution
J is free of metal M1 component, then individually adds the hydrochloric acid or nitric acid solution of M1, forms solution J；
(8) the desired amount of solution J is measured, is added dropwise in suspension I, reacts 0.5h after being added dropwise to complete again, obtain suspension K；
(9) suspension K is washed to neutrality, then is respectively washed 3 times with dehydrated alcohol and toluene, obtained powder drying and in nitrogen
High-temperature roasting under gas or argon atmosphere；
(10) if Co element has been reduced in step (8), then (9) step obtains the heterogeneous Co base of olefin hydroformylation and urges
Agent；If reduction reaction could not occur, then material synthesis gas, H should be used before the use2Or one of CO is gone back again
It is former.
2. heterogeneous Co base catalyst of a kind of olefin hydroformylation according to claim 1 and preparation method thereof, feature
It is in the method:
(1) alkene is a kind of monoolefine or mixed olefins, and carbon number is 6 ~ 12；
(2) the metal M1 is one of IA and Group IIA element or a variety of, is the one or more of Na, K, Mg, Ca and Sr；
(3) the metal M2 is mainly one of transition metal element or major element Ga, In, Sn, Sb and Bi or a variety of；Institute
It includes one of Cr, Mn, Fe, Ni, Cu, Zn, Mo, W, Ru, Rh, Pd, Pt, Au and Ag or a variety of for stating transition metal element；
(4) the nonmetallic A includes the one or more of P, B, N, Se, Te, F, C；
(5) carrier includes SBA-15, MCM-41, ZSM-5, Silicalite-1, carbon nanotube, active carbon, mesoporous oxidation
Aluminium, graphene etc. it is one or more, be characterized in high-specific surface area or on active component electronic property have certain influence,
Or with regular cellular structure, meet one or more of them feature.
3. heterogeneous Co base catalyst of a kind of olefin hydroformylation according to claim 1 and preparation method thereof, feature
It is that the catalyst is applied to slurry bed system, catalyst, which is easy to be separated and recovered from product, to be recycled；The catalyst simultaneously
It can be directly used for other suitable reactors such as fixed bed.
4. heterogeneous Co base catalyst of a kind of olefin hydroformylation according to claim 1 and preparation method thereof, feature
It is that the catalyst can be applied in the hydroformylation reaction of alpha alkene, internal olefin, cycloolefin.
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Cited By (4)
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| CN111359655A (en) * | 2020-04-27 | 2020-07-03 | 宁夏大学 | High-carbon olefin hydroformylation heterogeneous Co-based catalyst |
| CN112023958A (en) * | 2020-09-21 | 2020-12-04 | 宁夏大学 | CO hydrogenation catalyst and preparation method thereof |
| CN113477257A (en) * | 2021-06-10 | 2021-10-08 | 中科合成油技术有限公司 | Load type CoxMyIntermetallic compound catalysts, methods of making and using the same |
| CN114163318A (en) * | 2020-09-10 | 2022-03-11 | 中国科学院大连化学物理研究所 | Application of supported Rh monatomic catalyst in olefin hydroformylation reaction |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3940447A (en) * | 1970-04-27 | 1976-02-24 | Atlantic Richfield Company | Process for hydroformylation of olefin hydrocarbons |
| US20020111517A1 (en) * | 2001-02-13 | 2002-08-15 | Wolfgang Ahlers | Hydroformylation catalyst comprising a complex with ligands having a structure derived from bisphenol A |
| CN101085725A (en) * | 2007-07-10 | 2007-12-12 | 清华大学 | Method for preparing aldehydes from olefin and synthetic gas |
| CN102266796A (en) * | 2006-12-22 | 2011-12-07 | 中国科学院上海有机化学研究所 | Propylene hydroformylation catalyzing system and method |
| CN103521268A (en) * | 2012-07-03 | 2014-01-22 | 中国科学院大连化学物理研究所 | Heterogeneous catalysts for alkene hydroformylation reaction and preparation method thereof |
| CN104591960A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | Heterogeneous catalysis method for synthesizing aldehydes and alcohols through olefin hydroformylation, and apparatus thereof |
| CN104588057A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst for synthesizing aldehydes and alcohols through olefin hydroformylation, and preparation method thereof |
| US9283551B2 (en) * | 2013-01-23 | 2016-03-15 | Mississippi State University Research And Technology Corporation | Catalysts for converting syngas into liquid hydrocarbons and methods thereof |
| CN107042101A (en) * | 2017-06-02 | 2017-08-15 | 宁夏大学 | A kind of hydrogenation of carbon dioxide catalyst for methanol of doped graphene |
-
2019
- 2019-04-02 CN CN201910259362.5A patent/CN109821567B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3940447A (en) * | 1970-04-27 | 1976-02-24 | Atlantic Richfield Company | Process for hydroformylation of olefin hydrocarbons |
| US20020111517A1 (en) * | 2001-02-13 | 2002-08-15 | Wolfgang Ahlers | Hydroformylation catalyst comprising a complex with ligands having a structure derived from bisphenol A |
| CN102266796A (en) * | 2006-12-22 | 2011-12-07 | 中国科学院上海有机化学研究所 | Propylene hydroformylation catalyzing system and method |
| CN101085725A (en) * | 2007-07-10 | 2007-12-12 | 清华大学 | Method for preparing aldehydes from olefin and synthetic gas |
| CN103521268A (en) * | 2012-07-03 | 2014-01-22 | 中国科学院大连化学物理研究所 | Heterogeneous catalysts for alkene hydroformylation reaction and preparation method thereof |
| US9283551B2 (en) * | 2013-01-23 | 2016-03-15 | Mississippi State University Research And Technology Corporation | Catalysts for converting syngas into liquid hydrocarbons and methods thereof |
| CN104591960A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | Heterogeneous catalysis method for synthesizing aldehydes and alcohols through olefin hydroformylation, and apparatus thereof |
| CN104588057A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst for synthesizing aldehydes and alcohols through olefin hydroformylation, and preparation method thereof |
| CN107042101A (en) * | 2017-06-02 | 2017-08-15 | 宁夏大学 | A kind of hydrogenation of carbon dioxide catalyst for methanol of doped graphene |
Non-Patent Citations (3)
| Title |
|---|
| ZHANG, Y ET AL: "Preparation, characterization and catalytic hydroformylation properties of carbon nanotubes-supported Rh-phosphine catalyst", 《APPLIED CATALYSIS A-GENERAL》 * |
| 李金金 等: "非晶态Co-P-B催化剂在1-辛烯氢甲酰化反应中的应用", 《高等学校化学学报》 * |
| 范素兵 等: "MTP反应中调控双循环机理实现增产丙烯", 《天然气化工(C1化学与化工)》 * |
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|---|---|---|---|---|
| CN111359655A (en) * | 2020-04-27 | 2020-07-03 | 宁夏大学 | High-carbon olefin hydroformylation heterogeneous Co-based catalyst |
| CN114163318A (en) * | 2020-09-10 | 2022-03-11 | 中国科学院大连化学物理研究所 | Application of supported Rh monatomic catalyst in olefin hydroformylation reaction |
| CN114163318B (en) * | 2020-09-10 | 2023-04-18 | 中国科学院大连化学物理研究所 | Application of supported Rh monatomic catalyst in olefin hydroformylation reaction |
| CN112023958A (en) * | 2020-09-21 | 2020-12-04 | 宁夏大学 | CO hydrogenation catalyst and preparation method thereof |
| CN112023958B (en) * | 2020-09-21 | 2023-03-24 | 宁夏大学 | CO hydrogenation catalyst and preparation method thereof |
| CN113477257A (en) * | 2021-06-10 | 2021-10-08 | 中科合成油技术有限公司 | Load type CoxMyIntermetallic compound catalysts, methods of making and using the same |
| CN113477257B (en) * | 2021-06-10 | 2023-07-28 | 中科合成油技术股份有限公司 | Load type Co x M y Intermetallic catalyst, method of making and using the same |
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