CN109590012A - A kind of nitrogen-doped carbon cladding double nano metallic catalyst and its preparation method and application - Google Patents
A kind of nitrogen-doped carbon cladding double nano metallic catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of nitrogen-doped carbon cladding double nano metallic catalysts and its preparation method and application.The catalyst greatly improves catalyst to the selectivity and catalyst life of bata-phenethyl alcohol by auxiliary agent and the modification of carrier and the cladding of nitrogen-doped carbon compound.Catalyst prepared by the present invention is applied to the simple process of hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide, the continuous and steady operation under 70~80 DEG C, the relatively temperate condition of 3~4MPa, styrene oxide conversion ratio > 99.8%, bata-phenethyl alcohol selectivity > 99.5%, without adding other any auxiliary agents, solvent in reaction process, product separation is simple, and catalyst consumption is down to 0.8Kg(CAT)/t(PEA), be conducive to industrial amplification production.
Description
Technical field
The present invention relates to a kind of nitrogen-doped carbon cladding double nano metallic catalyst and preparation method thereof and for by Oxybenzene
Ethylene prepares the purposes of bata-phenethyl alcohol.
Background technique
Bata-phenethyl alcohol is a kind of simple aromatic alcohols, has simple and elegant, fine and smooth and lasting rose aroma, extensive
Applied to daily-use chemical industry kind, such as toner, perfumed soap, shampoo；Also it is used in edible essence and flavouring essence for tobacco, is to match
The primary raw material of rose scent food additives processed, rose scent essence；In addition, bata-phenethyl alcohol can also be used in Chemical Manufacture,
Such as pharmaceutical intermediate, fuel intermediate, fine perfumery intermediate, production status are closely related with human lives.
Natural benzyl carbinol has more soft lasting fragrance, higher commercial value, but it is in resource in nature
It is very limited.Therefore, bata-phenethyl alcohol currently on the market is substantially commercial synthesis.The main side of industrial production bata-phenethyl alcohol
Process optimization of the method successively through toluene method, epoxyethane method (Friedel-Crafts reaction) and styrene oxide hydrogenation method is made
For the main method for currently preparing bata-phenethyl alcohol, the homogeneous method and multi-phases process of hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide have
Document report.Homogeneous method is greatly hardly used due to product separating difficulty.In heterogeneous catalysis, skeleton Ni is the most frequently used
Catalyst.
US3579593 describes the method for making catalyst preparation bata-phenethyl alcohol with skeleton Ni and Pd respectively, is individually with Ni
When catalyst, the content of by-product ethylbenzene is up to 11%；When individually making catalyst with Pd, the content of by-product phenylacetaldehyde is up to
10%, the yield of bata-phenethyl alcohol is relatively low.
US6166269 is by the way that the alkaline assistants such as NaOH, the conversion ratio and β-benzene of styrene oxide are added into reaction system
The selectivity of ethyl alcohol reaches 99%, but the addition meeting of additive alkali is so that the problems such as generating stifled tower when late-stage products separate.
In CN1111169A, although the yield of bata-phenethyl alcohol is higher, the auxiliary agent being added in technical process be organic amine and
Alkaline matter has toxicity and equipment corrosion, and affects greatly to fragrance.
It proposes to make catalyst preparation β-benzene second under alkaline condition with water as solvent, Raney Ni or Co in US2822403
Alcohol, but a large amount of water of the process requirement, while emulsifier need to be added to adjust the compatibility of water and styrene oxide, after this is
The separation of phase product brings great difficulty.
In above-mentioned technology, there is that product yield is relatively low, product separation is difficult, it is short to add additive alkali, catalyst life,
Therefore the deficiencies of product fragrance is not pure develops a kind of efficiently highly selective catalyst, avoids addition auxiliary agent and promote catalysis
The bata-phenethyl alcohol production technology in agent service life is of great significance.
Summary of the invention
The object of the present invention is to provide a kind of catalyst for being used to prepare bata-phenethyl alcohol, which has excellent activity
And selectivity, it is provided simultaneously with longer catalytic life.
According to the first aspect of the invention, a kind of nitrogen-doped carbon cladding double nano metallic catalyst is provided comprising negative
Catalyst activity component Ni, the Co element and auxiliary agent being loaded in amine Modified MCM-41 mesopore molecular sieve carrier, and it is scattered in amine
The nitrogen-doped carbon compound of clad is formed in Modified MCM-41 mesopore molecular sieve carrier and to active component, wherein
Ni element: content is 10~25wt%, preferably 15~20wt%, in terms of element Ni；
Co element: content is 5~20wt%, preferably 10~15wt%, in terms of Elements C o；
Auxiliary agent: content is 2~10wt%, preferably 4~5wt%, in elemental metal, including Zn, Mg, La and Ce element
It is one or more, preferably comprise Zn and Ce element, more preferably the molar ratio of Zn and Ce element is 1~2:1；
Clad: nitrogen-doped carbon compounds content is 15~30wt%, preferably 20~25wt%, in terms of carbonitride；
Carrier: amine Modified MCM-41 15~68wt% of mesopore molecular sieve, preferably 35~51wt%, with SiO2Meter；
It is above the weight based on catalyst.
In catalyst, active component, adjuvant component exist in the form of an oxide, exist after carrying out reduction with element form,
Metering makees benchmark with element.
Wherein, nitrogen-doped carbon compound is the compound such as melamine of for example carbon containing nitrogen of nitrogen-doped carbon compound precursor
One of amine, urea, uracil or it is a variety of under atmosphere of inert gases roasting (such as at 350~450 DEG C roast 6-15 it is small
When) and the product of formation.It is represented by n-C3N4, and the difference with carbonitride C3N4 is that its C/N ratio is only ideal C3N4
Hereinafter, i.e. n is generally 0.4~0.6, specific ratio is related with after baking environment for the 0.6 of ratio.After baking temperature is higher, n
It is worth higher.
Catalyst activity component Ni, Co of the present invention is carried in amine Modified MCM-41 mesopore molecular sieve carrier, is led to
It crosses introducing nitrogen-doped carbon compound and clad structure is formed to active component.
According to the second aspect of the invention, invention further provides the preparation methods of above-mentioned catalyst, including with
Lower step:
(A) amine Modified MCM-41 mesopore molecular sieve mother liquor is prepared；
(B) active component presoma, auxiliary agent presoma are mixed with MCM-41 mesopore molecular sieve mother liquor；
It (C) will be in the compound of for example carbon containing nitrogen of nitrogen-doped carbon compound precursor such as melamine, urea, uracil
One or more heated in atmosphere of inert gases obtain nitrogen-doped carbon compound, by infusion process by nitrogen-doped carbon compound point
It dissipates in molecular sieve and clad structure is formed to active component；
(D) step (C) products therefrom is formed.
In a more specific embodiment, above-mentioned catalyst preparation method the following steps are included:
1) by the presoma of active component Ni, Co element (usual Ni salt, Co salt), auxiliary agent presoma (Zn, Mg, La and Ce
The salt of one of element or multiple element) it is dissolved in the water, aqueous solution is preferably formed in deionized water, preferably each precursor salt
It is 1~30wt% in the concentration of aqueous solution, all presomas can be added to the water to form water together by preferably 3~15wt%
Solution can also prepare the aqueous solution of each presoma；
2) the step 1) aqueous solution mixing is added in amine Modified MCM-41 mesopore molecular sieve mother liquor (such as persistently to stir
It mixes)；
3) by nitrogen-doped carbon compound precursor (such as the compound such as melamine of carbon containing nitrogen, urea, in uracil
One or more, preferably melamine or melamine) be placed in heating under (such as in crucible with cover) inert environments (such as 350
Roasted 6-15 hours at~450 DEG C), obtain solid, grind into powder state；
4) the resulting powder of step 3) is added in mixed solution obtained by step 2) under the conditions of strong mixing, is preferably passed through
Ultrasonic power is reinforced powder and is penetrated into active component；
5) by the removal of mixed liquor obtained by step 4) solvent (such as by moving in vacuum freezing drying oven), then by solid
Powder (such as being transferred in crucible) roasting；
6) step 5) obtained solid powder is obtained into spheric granules (granularity model in the way of roller forming by binder
Enclosing 10-100 mesh) catalyst is spare.
The active component presoma, amine Modified MCM-41 mesopore molecular sieve, the respective use of nitrogen-doped carbon compound precursor
Amount should make, and in prepared catalyst, in terms of metal element content, Ni element accounts for 10~35wt% of made catalyst,
It is preferred that 20~25wt%, Co element account for 5~20wt% of made catalyst, preferably 10~15wt%, auxiliary agent content is 2~
10wt%, preferably 4~6wt%, nitrogen-doped carbon compounds content are 20~35wt%, preferably 25~30wt%, in terms of carbonitride；
Amine Modified MCM-41 15~68wt% of mesopore molecular sieve, preferably 35~51wt%.
Preferably, in the preparation method step 1) of catalyst of the present invention, the active component presoma is Ni
(NO3)2·6H2O and Co (NO3)2·6H2O, the auxiliary agent presoma are selected from Zn (NO3)2·6H2O、Mg(NO3)2·6H2O、La
(NO3)3·6H2O、Ce(NO3)3·6H2One of O or a variety of preferably comprises Zn (NO3)2·6H2O and Ce (NO3)3·
6H2O, the more preferably molar ratio of Zn and Ce element are 1~2:1；Zn and Ce element total content account for made catalyst 2~
10wt%, preferably 4~6wt%.
In the present invention, the dosage of water is active component presoma Ni (NO in the step 1) aqueous solution3)2·6H2O and Co
(NO3)2·6H21.5-10 times of O gross mass, preferably from about 2 times；To guarantee active component presoma and auxiliary agent presoma
It is sufficiently mixed, the active component presoma and auxiliary agent is preferably controlled in the preparation method step 1) of heretofore described catalyst
The incorporation time of presoma is 2~5h, preferably 3~4h.
In the preparation method step (A) or step 2) of catalyst of the present invention, the amine Modified MCM-41 mesoporous molecular
Sieve mother liquor is the preparation method comprises the following steps: that tetraethyl orthosilicate is added dropwise to cetyl trimethylammonium bromide (CTAB) under strong agitation is water-soluble
In liquid (10~40wt% of concentration range, preferably 15-25wt%), so that concentration of the ethyl orthosilicate in CTAB aqueous solution is
50-80wt%, preferably 65~75wt%, and be added and reach 5~15wt%, preferably 8~12wt% in CTAB aqueous solution, such as
The triethylene diamine of 10wt% sufficiently dissolves, then be added the preferred NaOH aqueous solution of alkali (5~20wt% of concentration range, preferably from about
10wt%) adjusting pH to 9~11, heat preservation a period of time (such as in pressure hydrothermal reaction kettle certainly (40~100 DEG C of temperature, preferably 60
~80 DEG C；0.1~0.5MPa of pressure, preferably from about 0.2-0.4MPa) constant temperature 5-24 hours, preferably 12h) change to get to the amine
Property MCM-41 mesopore molecular sieve mother liquor (in mother liquor, solid content is generally 10-50wt%).
In the present invention, the step 2) aqueous solution and amine Modified MCM-41 mesopore molecular sieve mother liquor mixing time are 3
~8h, preferably 4~5h.
In the preparation method step 3) of catalyst of the present invention, the heating temperature be 400~600 DEG C, preferably 500~
550 DEG C, 4~10h of heating time, preferably 6~8h.
In the preparation method step 4) of catalyst of the present invention, the ultrasonic temperature be 40~80 DEG C, preferably 50~60
℃；The ultrasonic time is 1~4h, preferably 2~3h.
In the preparation method step 5) of catalyst of the present invention, the vacuum freezing drying oven drying temperature be 90~
120 DEG C, preferably 100~110 DEG C, drying time be 12~for 24 hours, preferably 15~20h；The baking modes are in a nitrogen atmosphere
800~1000 DEG C, preferably 850~900 DEG C are heated to the rate of 2.5 DEG C/min, and keep 1~4h, preferably 2~3h.
In the preparation method step 6) of catalyst of the present invention, the binder is aluminium oxide or silica solution, preferably silicon
Colloidal sol；The catalyst particle size preferably 40~60 mesh, binder relative to the solid powder of step 5) dosage 10~
40%, preferably 20~25wt%.
According to the third aspect of the present invention, the present invention also provides above-mentioned nitrogen-doped carbons to coat double nano metallic catalyst
For by the purposes of hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide.
According to the fourth aspect of the present invention, the present invention provides coat double nano metal catalytic using above-mentioned nitrogen-doped carbon
The method of agent progress hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide, comprising the following steps:
1) load catalyst in fixed bed, upper and lower level loads the quartz sand of 20~40 mesh, be passed through hydrogen to catalyst into
Row reduction；
2) at 60~90 DEG C, the hydrogen pressure of preferably 70~80 DEG C of hydrogenation reaction temperature and 1~5MPa, preferably 3~4MPa
It is pumped into raw material styrene oxide under power (absolute pressure) and carries out hydrogenation reaction generation bata-phenethyl alcohol.
Reactor used in the present invention is fixed bed reactors, in reaction process the air speed of styrene oxide be 1~
10h-1, preferably 5~7.5-1。
The beneficial effects of the present invention are:
Nitrogen-doped carbon cladding double nano metallic catalyst of the present invention is made by the collaboration of double activated component nano metal
With ensureing the activity of catalyst；Meanwhile the clad structure of nitrogen-doped carbon compound is introduced in the catalyst, avoid Oxybenzene second
Alkene epoxide epoxy group group, which is directly contacted with catalyst activity position, to be occurred the big weight phenylethylene of deoxygenation generation and then is hydrogenated to ethylbenzene；
By the adjusting of auxiliary agent and amine modified support, a possibility that benzene ring hydrogenation reacts is reduced, bata-phenethyl alcohol is reduced and further adds hydrogen
Possibility.Therefore, while the introducing for avoiding alkaline assistant, modification and clad structure by auxiliary agent and carrier, greatly
Improve the selectivity of bata-phenethyl alcohol.
Loss of the catalyst of the present invention by the effective inhibitory activity component of cladding of nitrogen-doped carbon compound, catalyst
Service life is long, and unit consumption is low, greatly reduces production cost.
The simple process of hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide of the present invention, without adding other in reaction process
Any auxiliary agent, solvent, and reaction condition is mild, product separation is simple, is easy to industrial amplification production.
Specific embodiment
Embodiment 1
Weigh the Ni (NO of 49.3g3)2·6H2O, the Co (NO of 98.6g3)2·6H2O, the ZnNO of 11.4g3)2·6H2O、
Mg (the NO of 26.7g3)2·6H2O, the La (NO of 7.8g3)3·6H2Ce (the NO of O and 7.8g3)3·6H2O is simultaneously added thereto
The deionized water wiring solution-forming of 295.9g is sufficiently stirred 2h and forms solution 1；The TEOS (ethyl orthosilicate) of 156.0g is added to
In CTAB (cetyl trimethylammonium bromide) solution of 222g 10wt%, and the triethylene diamine shape of 22.2g is added thereto
Stirring 3h is sufficiently mixed at MCM-41 mesopore molecular sieve mother liquor, and by solution 1 and molecular sieve mother liquor；Weigh the melamine of 18.9g
Amine forms solid powder in 400 DEG C of heating 10h under argon atmosphere, this fixation powder is added in above-mentioned mixed liquor in 40 DEG C
Lower ultrasound 4h, take out mixed liquor move to vacuum freezing drying oven at 90 DEG C it is dry for 24 hours, then in a nitrogen atmosphere with 2.5 DEG C/
The rate of min is heated to 800 DEG C of roasting 4h and obtains solid catalyst first product.50g solid catalyst powder is taken, with 5g aluminium oxide work
Catalyst first product is obtained that 40~60 mesh spheric granules catalyst are spare, and catalyst is named as by binder through the mode of roller forming
CAT1-Al, Ni content 10wt%, Co content 20wt%, Zn content 2.5wt%, Mg content 2.5wt%, La in final catalyst
Content 2.5wt%, Ce content 2.5wt%, nitrogen-doped carbon compounds content 15wt%, remaining is amine Modified MCM-41 mesoporous molecular
Sieve.
Catalyst CAT1-Al is used in hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide fixed-bed process: weighing the catalysis
Agent 20g is filled in the middle part of reactor, and upper and lower level loads the quartz sand of 20~40 mesh, is passed through hydrogen and is restored to catalyst, also
Former temperature is 550 DEG C, recovery time 5h, 60 DEG C of set temperature, pressure 5MPa, styrene oxide air speed 10h-1It carries out continuous steady
Fixed operating.
Embodiment 2
Weigh the Ni (NO of 123.3g3)2·6H2O, the Co (NO of 24.7g3)2·6H2The ZnNO of O and 9.1g3)2·6H2O is simultaneously
The deionized water wiring solution-forming of 295.9g is added thereto, 5h is sufficiently stirred and forms solution 1；The TEOS of 131.7g is added to
In the CTAB solution of 188g 40%, and the triethylene diamine that 18.8g is added thereto forms MCM-41 mesopore molecular sieve mother liquor,
And solution 1 and molecular sieve mother liquor are sufficiently mixed stirring 8h；The melamine for weighing 37.8g adds under argon atmosphere in 600 DEG C
Hot 4h forms solid powder, this fixation powder is added in above-mentioned mixed liquor the ultrasound 1h at 80 DEG C, mixed liquor is taken out and moves to
Vacuum freezing drying oven dry 12h at 120 DEG C, is then heated to 1000 DEG C in a nitrogen atmosphere with the rate of 2.5 DEG C/min
Roasting 1h obtains solid catalyst first product.50g solid catalyst powder is taken, binder is made for catalyst first product with 20g aluminium oxide
Mode through roller forming obtains that 40~60 mesh spheric granules catalyst are spare, and catalyst is named as CAT2-Al.
Ni content 25wt%, Co content 5wt%, Zn content 2wt% in final catalyst, nitrogen-doped carbon compounds content
30wt%, remaining is amine Modified MCM-41 mesopore molecular sieve.
Catalyst CAT2-Al is used in hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide fixed-bed process: weighing the catalysis
Agent 20g is filled in the middle part of reactor, and upper and lower level loads the quartz sand of 20~40 mesh, is passed through hydrogen and is restored to catalyst, also
Former temperature is 200 DEG C, recovery time 1h, 90 DEG C of set temperature, pressure 1MPa, styrene oxide air speed 1h-1It carries out continuous steady
Fixed operating.
Embodiment 3
Weigh the Ni (NO of 74.0g3)2·6H2O, the Co (NO of 74.0g3)2·6H2The LaNO of O and 15.6g3)3·6H2O is simultaneously
The deionized water wiring solution-forming of 295.9g is added thereto, 2.5h is sufficiently stirred and forms solution 1；The TEOS of 156.0g is added to
In the CTAB solution of 222g 20%, and the triethylene diamine that 22.2g is added thereto forms MCM-41 mesopore molecular sieve mother liquor,
And solution 1 and molecular sieve mother liquor are sufficiently mixed stirring 4h；The melamine for weighing 25.2g adds under argon atmosphere in 450 DEG C
Hot 5h forms solid powder, this fixation powder is added in above-mentioned mixed liquor the ultrasound 1.5h at 50 DEG C, mixed liquor is taken out and moves
14h is dried at 95 DEG C to vacuum freezing drying oven, is then heated to 850 DEG C in a nitrogen atmosphere with the rate of 2.5 DEG C/min
Roasting 1.5h obtains solid catalyst first product.50g solid catalyst powder is taken, making binder with 10g aluminium oxide will be at the beginning of catalyst
Product obtain that 40~60 mesh spheric granules catalyst are spare, and catalyst is named as CAT3-Al through the mode of roller forming.
Ni content 15wt%, Co content 15wt%, La content 5wt% in final catalyst, nitrogen-doped carbon compounds content
20wt%, remaining is amine Modified MCM-41 mesopore molecular sieve.
Catalyst CAT3-Al is used in hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide fixed-bed process: weighing the catalysis
Agent 20g is filled in the middle part of reactor, and upper and lower level loads the quartz sand of 20~40 mesh, is passed through hydrogen and is restored to catalyst, also
Former temperature is 300 DEG C, recovery time 3h, 70 DEG C of set temperature, pressure 4MPa, styrene oxide air speed 7.5h-1It carries out continuous
Steady running.
Embodiment 4
Weigh the Ni (NO of 123.3g3)2·6H2O, the Co (NO of 49.3g3)2·6H2Ce (the NO of O and 15.5g3)3·6H2O
And the deionized water wiring solution-forming of 345.3g is added thereto, 4.5h is sufficiently stirred and forms solution 1；The TEOS of 104.0g is added
Into the CTAB solution of 148g 20%, and the triethylene diamine that 14.8g is added thereto forms MCM-41 mesopore molecular sieve mother
Liquid, and solution 1 and molecular sieve mother liquor are sufficiently mixed stirring 7h；The melamine of 37.8g is weighed under argon atmosphere in 550 DEG C
It heats 9h and forms solid powder, this fixation powder is added in above-mentioned mixed liquor the ultrasound 3.5h at 70 DEG C, takes out mixed liquor
Vacuum freezing drying oven dry 20h at 115 DEG C is moved to, is then heated to 950 in a nitrogen atmosphere with the rate of 2.5 DEG C/min
DEG C roasting 3.5h obtain solid catalyst first product.50g solid catalyst powder is taken, binder is made for catalyst with 10g aluminium oxide
First product obtains that 40~60 mesh spheric granules catalyst are spare, and catalyst is named as CAT4-Al through the mode of roller forming.
Ni content 25wt%, Co content 10wt%, Ce content 5wt% in final catalyst, nitrogen-doped carbon compounds content
30wt%, remaining is amine Modified MCM-41 mesopore molecular sieve.
Catalyst CAT4-Al is used in hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide fixed-bed process: weighing the catalysis
Agent 20g is filled in the middle part of reactor, and upper and lower level loads the quartz sand of 20~40 mesh, is passed through hydrogen and is restored to catalyst, also
Former temperature is 400 DEG C, recovery time 2h, 80 DEG C of set temperature, pressure 2MPa, styrene oxide air speed 5h-1It carries out continuous steady
Fixed operating.
Embodiment 5
Weigh the Ni (NO of 74.0g3)2·6H2O, the Co (NO of 74.0g3)2·6H2O, the ZnNO of 13.7g3)2·6H2O、
Mg (the NO of 16.0g3)2·6H2Ce (the NO of O and 4.7g3)3·6H2O and the deionized water that 295.9g is added thereto are made into molten
Liquid is sufficiently stirred 3h and forms solution 1；The TEOS of 135.2g is added in the CTAB solution of 193g 20%, and is added thereto
The triethylene diamine of 19.3g forms MCM-41 mesopore molecular sieve mother liquor, and solution 1 and molecular sieve mother liquor are sufficiently mixed stirring
5h；The melamine for weighing 31.5g forms solid powder in 500 DEG C of heating 6h under argon atmosphere, this is fixed powder and is added
Into above-mentioned mixed liquor, ultrasound 2h, taking-up mixed liquor move to vacuum freezing drying oven dry 15h at 100 DEG C at 55 DEG C, with
900 DEG C of roasting 2h are heated to the rate of 2.5 DEG C/min in a nitrogen atmosphere afterwards and obtain solid catalyst first product.Take 50g solid
Catalyst fines, by 10g aluminium oxide make binder by catalyst first product through roller forming in a manner of obtain spherical, 40~60 mesh
Grain catalyst is spare, and catalyst is named as CAT5-Al.
Ni content 15wt%, Co content 15wt%, Zn content 3wt%, Mg content 1.5wt%, Ce contain in final catalyst
1.5wt%, nitrogen-doped carbon compounds content 25wt% are measured, remaining is amine Modified MCM-41 mesopore molecular sieve.
Catalyst CAT5-Al is used in hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide fixed-bed process: weighing the catalysis
Agent 20g is filled in the middle part of reactor, and upper and lower level loads the quartz sand of 20~40 mesh, is passed through hydrogen and is restored to catalyst, also
Former temperature is 350 DEG C, recovery time 3h, 70 DEG C of set temperature, pressure 3MPa, styrene oxide air speed 5h-1It carries out continuous steady
Fixed operating.
Embodiment 6
Weigh the Ni (NO of 74.0g3)2·6H2O, the Co (NO of 49.3g3)2·6H2O, the Mg (NO of 15.4g3)2·6H2O and
Ce (the NO of 5.0g3)3·6H2O and the deionized water wiring solution-forming that 246.6g is added thereto are sufficiently stirred 4h and form solution 1；
The TEOS of 176.8g is added in the CTAB solution of 252g 20%, and the triethylene diamine that 25.2g is added thereto is formed
MCM-41 mesopore molecular sieve mother liquor, and solution 1 and molecular sieve mother liquor are sufficiently mixed stirring 6h；Weigh the melamine of 25.2g
Solid powder is formed in 550 DEG C of heating 8h under argon atmosphere, this fixation powder is added in above-mentioned mixed liquor at 65 DEG C
Ultrasonic 2.5h takes out mixed liquor and moves to vacuum freezing drying oven dry 18h at 110 DEG C, then in a nitrogen atmosphere with 2.5
DEG C/rate of min is heated to 850 DEG C of roasting 3h and obtains solid catalyst first product.50g solid catalyst powder is taken, is aoxidized with 10g
Aluminium makees binder catalyst first product obtained 40~60 mesh spheric granules catalyst through the mode of roller forming spare, catalyst life
Entitled CAT6-Al.
Ni content 15wt%, Co content 10wt%, Mg content 2.4wt%, Ce content 1.6wt% in final catalyst, nitrogen
Doped carbon compounds content 20wt%, remaining is amine Modified MCM-41 mesopore molecular sieve.
Catalyst CAT6-Al is used in hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide fixed-bed process: weighing the catalysis
Agent 20g is filled in the middle part of reactor, and upper and lower level loads the quartz sand of 20~40 mesh, is passed through hydrogen and is restored to catalyst, also
Former temperature is 350 DEG C, recovery time 3h, 70 DEG C of set temperature, pressure 4MPa, styrene oxide air speed 5h-1It carries out continuous steady
Fixed operating.
Embodiment 7
Weigh the Ni (NO of 98.6g3)2·6H2O, the Co (NO of 74.0g3)2·6H2O, the Zn (NO of 11.4g3)2·6H2O and
La (the NO of 7.8g3)3·6H2O and the deionized water wiring solution-forming that 345.3g is added thereto are sufficiently stirred 3.5h and form solution
1；The TEOS of 121.3g is added in the CTAB solution of 173g 20%, and the triethylene diamine that 17.3g is added thereto is formed
MCM-41 mesopore molecular sieve mother liquor, and solution 1 and molecular sieve mother liquor are sufficiently mixed stirring 4h；Weigh the melamine of 31.5g
Solid powder is formed in 500 DEG C of heating 7h under argon atmosphere, this fixation powder is added in above-mentioned mixed liquor at 60 DEG C
Ultrasonic 3h takes out mixed liquor and moves to vacuum freezing drying oven dry 16h at 105 DEG C, then in a nitrogen atmosphere with 2.5 DEG C/
The rate of min is heated to 850 DEG C of roasting 2.5h and obtains solid catalyst first product.50g solid catalyst powder is taken, is aoxidized with 10g
Aluminium makees binder catalyst first product obtained 40~60 mesh spheric granules catalyst through the mode of roller forming spare, catalyst life
Entitled CAT7-Al.
Ni content 20wt%, Co content 15wt%, Zn content 2.5wt%, La content 2.5wt% in final catalyst, nitrogen
Doped carbon compounds content 25wt%, remaining is amine Modified MCM-41 mesopore molecular sieve.
Catalyst CAT7-Al is used in hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide fixed-bed process: weighing the catalysis
Agent 20g is filled in the middle part of reactor, and upper and lower level loads the quartz sand of 20~40 mesh, is passed through hydrogen and is restored to catalyst, also
Former temperature is 350 DEG C, recovery time 3h, 80 DEG C of set temperature, pressure 3MPa, styrene oxide air speed 5h-1It carries out continuous steady
Fixed operating.
Embodiment 8
Weigh the Ni (NO of 98.6g3)2·6H2O, the Co (NO of 49.3g3)2·6H2O, the Zn (NO of 13.7g3)2·6H2O and
Ce (the NO of 6.2g3)3·6H2O and the deionized water wiring solution-forming that 295.9g is added thereto are sufficiently stirred 3.5h and form solution
1；The TEOS of 156.0g is added in the CTAB solution of 222g 20%, and the triethylene diamine that 22.2g is added thereto is formed
MCM-41 mesopore molecular sieve mother liquor, and solution 1 and molecular sieve mother liquor are sufficiently mixed stirring 4.5h；Weigh the melamine of 25.2g
Amine forms solid powder in 550 DEG C of heating 7h under argon atmosphere, this fixation powder is added in above-mentioned mixed liquor in 60 DEG C
Lower ultrasound 3h takes out mixed liquor and moves to vacuum freezing drying oven dry 16h at 105 DEG C, then in a nitrogen atmosphere with 2.5
DEG C/rate of min is heated to 900 DEG C of roasting 2.5h and obtains solid catalyst first product.50g solid catalyst powder is taken, with 10g oxygen
Change aluminium and makees binder catalyst first product obtained into 40~60 mesh spheric granules catalyst through the mode of roller forming spare, catalyst
It is named as CAT8-Al.
Ni content 20wt%, Co content 10wt%, Zn content 3wt%, Ce content 2wt% in final catalyst, N doping
Carbon compound content 20wt%, remaining is amine Modified MCM-41 mesopore molecular sieve.
Catalyst CAT8-Al is used in hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide fixed-bed process: weighing the catalysis
Agent 20g is filled in the middle part of reactor, and upper and lower level loads the quartz sand of 20~40 mesh, is passed through hydrogen and is restored to catalyst, also
Former temperature is 350 DEG C, recovery time 3h, 70 DEG C of set temperature, pressure 4MPa, styrene oxide air speed 5h-1It carries out continuous steady
Fixed operating.
Comparative example 1~8
The binder of the roller forming of Examples 1 to 8 is changed to silica solution respectively, catalyst is successively named as CAT1~8-
Si, and in hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide fixed-bed process under corresponding equal conditions.
Experimental evaluation the results are shown in Table 1.
Table 1 prepares benzyl carbinol continuous processing and batch technology evaluation result
Using the modified catalyst of the present invention, auxiliary agent, solvent are not being added additionally, is using the fixed-bed process after optimization
Under the conditions of, acquisition bata-phenethyl alcohol that can be highly selective.Relative to other catalyst, the modified catalyst of the present invention is due to having
The synergistic effect of double activated component nano metal, ensures the activity of catalyst；Pass through modification and the nitrogen of auxiliary agent and carrier simultaneously
The clad structure for adulterating carbon compound, greatly improves the selectivity of bata-phenethyl alcohol.
Compared to comparative example, the service life is longer by the optimization resulting catalyst of binder by the present invention, catalyst consumption
It is lower, minimum reachable 0.8Kg(CAT)/t(PEA)。
Claims (10)
1. a kind of nitrogen-doped carbon coats double nano metallic catalyst comprising be carried on amine Modified MCM-41 mesopore molecular sieve carrier
In catalyst activity component Ni, Co element and auxiliary agent, and be scattered in it is in amine Modified MCM-41 mesopore molecular sieve carrier and right
The nitrogen-doped carbon compound of active component formation clad, wherein
Ni element: content is 10~25wt%, preferably 15~20wt%, in terms of element Ni；
Co element: content is 5~20wt%, preferably 10~15wt%, in terms of Elements C o；
Auxiliary agent: content is 2~10wt%, preferably 4~5wt%, with elemental metal, including one in Zn, Mg, La and Ce element
Kind is a variety of, preferably comprises Zn and Ce element, and the more preferably molar ratio of Zn and Ce element is 1~2:1；
Clad: nitrogen-doped carbon compound, content are 15~30wt%, preferably 20~25wt%, in terms of carbonitride；
Carrier: amine Modified MCM-41 15~68wt% of mesopore molecular sieve, preferably 35~51wt%, with SiO2Meter；
The above wt% is the weight based on catalyst.
2. nitrogen-doped carbon according to claim 1 coats double nano metallic catalyst, wherein nitrogen-doped carbon compound is nitrogen
One of compound such as melamine, urea, uracil of for example carbon containing nitrogen of doped carbon compound precursor or it is a variety of
The product for roasting (such as roasting 6-15 hours at 350~450 DEG C) under atmosphere of inert gases and being formed.
3. the preparation method of nitrogen-doped carbon cladding double nano metallic catalyst of any of claims 1 or 2, comprising the following steps:
(A) amine Modified MCM-41 mesopore molecular sieve mother liquor is prepared；
(B) active component presoma, auxiliary agent presoma are mixed with MCM-41 mesopore molecular sieve mother liquor；
(C) nitrogen-doped carbon compound precursor is heated in atmosphere of inert gases and obtains nitrogen-doped carbon compound, it will by infusion process
Nitrogen-doped carbon compound is scattered in molecular sieve and forms clad structure to active component；
(D) step (C) products therefrom is formed.
4. the preparation method of nitrogen-doped carbon cladding double nano metallic catalyst of any of claims 1 or 2, comprising the following steps:
1) by the presoma of active component Ni, Co element (usual Ni salt, Co salt), auxiliary agent presoma (Zn, Mg, La and Ce element
One of or multiple element salt) be dissolved in the water, aqueous solution is preferably formed in deionized water, preferably each precursor salt is in water
The concentration of solution is 1~30wt%, preferably 3~15wt%；
2) the step 1) aqueous solution is added in amine Modified MCM-41 mesopore molecular sieve mother liquor and is mixed；
3) nitrogen-doped carbon compound precursor is placed under inert environments and is heated, obtain solid, grind into powder state；
4) the resulting powder of step 3) is added in mixed solution obtained by step 2) under the conditions of strong mixing, preferably passes through ultrasound
Mode is reinforced powder and is penetrated into active component；
5) mixed liquor obtained by step 4) is removed into solvent, then roasts solid powder；
6) that step 5) obtained solid powder is obtained spheric granules catalyst in the way of roller forming by binder is spare.
5. the preparation method according to claim 4, wherein mesoporous point of the active component presoma, amine Modified MCM-41
Son sieve, the respective dosage of nitrogen-doped carbon compound precursor should make, in prepared catalyst, in terms of metal element content,
Ni element accounts for 10~25wt% of made catalyst, preferably 15~20wt%, and Co element accounts for 5~20wt% of made catalyst,
It is preferred that 10~15wt%, auxiliary agent content is 2~10wt%, preferably 4~5wt%, nitrogen-doped carbon compounds content is 15~
30wt%, preferably 20~25wt%, in terms of n-C3N4, n is 0.4~0.6；Amine Modified MCM-41 mesopore molecular sieve 15~
68wt%, preferably 35~51wt%.
6. preparation method described in any one of claim 4-5, wherein in step 1), the active component presoma is Ni
(NO3)2·6H2O and Co (NO3)2·6H2O, the auxiliary agent presoma are selected from Zn (NO3)2·6H2O、Mg(NO3)2·6H2O、La
(NO3)3·6H2O、Ce(NO3)3·6H2One of O or a variety of preferably comprises Zn (NO3)2·6H2O and Ce (NO3)3·
6H2O, the more preferably molar ratio of Zn and Ce element are 1~2:1；Zn and Ce element total content account for made catalyst 2~
10wt%, preferably 4~6wt%；And/or
The dosage of water is active component presoma Ni (NO in the step 1) aqueous solution3)2·6H2O and Co (NO3)2·6H2O is total
1.5-10 times of quality, preferably from about 2 times.
7. the preparation method according to any one of claim 3-6, wherein step (A) or 2) in, the amine modified MC M-
41 mesopore molecular sieve mother liquors are the preparation method comprises the following steps: be added dropwise to cetyl trimethylammonium bromide for tetraethyl orthosilicate under strong agitation
(CTAB) it in aqueous solution (concentration range general 10~40wt%, preferably 15-25wt%), and is added and reaches in CTAB aqueous solution
5~15wt%, preferably 8~12wt%, such as the triethylene diamine of 10wt% sufficiently dissolve, and it is water-soluble that the preferred NaOH of alkali is then added
Liquid (general 5~20wt% of concentration range, preferably from about 10wt%) adjusting pH to 9~11, heat preservation a period of time (such as in pressure water certainly
In thermal response kettle (such as (40~100 DEG C of temperature, preferably 60~80 DEG C in pressure hydrothermal reaction kettle certainly；0.1~0.5MPa of pressure,
Preferably from about 0.2-0.4MPa) constant temperature 5-24 hours, preferably 12h) to get arrive the amine Modified MCM-41 mesopore molecular sieve mother liquor
(in mother liquor, solid content is generally 10-50wt%).
8. the preparation method according to any one of claim 4-7, wherein the step 2) aqueous solution and amine modified MC M-
41 mesopore molecular sieve mother liquor mixing times are 3~8h, preferably 4~5h；And/or
In step 3), the heating temperature be 400~600 DEG C, preferably 500~550 DEG C, 4~10h of heating time, preferably 6~
8h；And/or
In step 4), the ultrasonic temperature is 40~80 DEG C, preferably 50~60 DEG C；The ultrasonic time be 1~4h, preferably 2~
3h；And/or
In step 5), removal solvent carried out in vacuum freezing drying oven, drying temperature be 90~120 DEG C, preferably 100~110
DEG C, drying time be 12~for 24 hours, preferably 15~20h；The baking modes are in a nitrogen atmosphere with the rate of 2.5 DEG C/min
800~1000 DEG C, preferably 850~900 DEG C are heated to, and keep 1~4h, preferably 2~3h；And/or
In step 6), the binder is aluminium oxide or silica solution, preferably silica solution；The catalyst particle size preferably 40~
60 mesh, binder 10~40wt% of dosage relative to the solid powder of step 5), preferably 20~25wt%.
9. nitrogen-doped carbon that is of any of claims 1 or 2 or being obtained by preparation method described in any one of claim 3-8
Double nano metallic catalyst is coated to be used for the purposes of hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide.
10. a kind of method of hydrogenation preparing bata-phenethyl alcohol from phenylethylene oxide, comprising the following steps:
1) it loads in fixed bed described in claim 1 or is obtained by preparation method described in any one of claim 2-8
The nitrogen-doped carbon obtained coats double nano metallic catalyst, and upper and lower level loads the quartz sand of 20~40 mesh, is passed through hydrogen to catalyst
It is restored；
2) at 60~90 DEG C, preferably 70~80 DEG C of hydrogenation reaction temperature and 1~5MPa, the preferably Hydrogen Vapor Pressure of 3~4MPa are (absolutely
To pressure) under be pumped into raw material styrene oxide carry out hydrogenation reaction generate bata-phenethyl alcohol.
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