CN106693992A - Hydrofining catalyst as well as preparation method and application thereof - Google Patents
Hydrofining catalyst as well as preparation method and application thereof Download PDFInfo
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- CN106693992A CN106693992A CN201710034646.5A CN201710034646A CN106693992A CN 106693992 A CN106693992 A CN 106693992A CN 201710034646 A CN201710034646 A CN 201710034646A CN 106693992 A CN106693992 A CN 106693992A
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- metal alloy
- hydrobon catalyst
- caprolactam
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- 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
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/16—Separation or purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a hydrofining catalyst which comprises an active substance outer surface layer and a metal alloy core, wherein the active substance outer surface layer is of a sponge-shaped porous structure; the metal alloy core is of a dense structure; the hydrofining catalyst comprises the following elements: 40-65wt% of Ni, 35-60wt% of Al, 0.1-2wt% of Nb and 0-10wt% of a modified metal element M. Compared with the prior art, the hydrofining catalyst is simple to prepare, high in activity, long in service life and relatively high in activity in high-concentration caprolactam hydrofining, the production energy consumption can be reduced, the production cost can be remarkably lowered, and the economic benefits can be increased.
Description
Technical field
The present invention relates to field of catalyst preparation, more particularly to a kind of caprolactam used in fixed bed reactors
Hydrobon catalyst and its preparation method and application.
Background technology
Caprolactam is a kind of important industrial chemicals, mainly for the production of nylon -6 fiber, nylon-6 engineering plastics and
Film, additionally, caprolactam can also be used to produce Laurocapram and antiplatelet drug 6-aminocaprolc acid etc., purposes is very wide
It is general.
At present, the conventional production methods of caprolactam mainly have cyclohexanone-azanol technique, hexamethylene photonitrosation technique with
And toluene technique, although domestic and foreign scholars develop many new production technologies in recent years, lacking for practical application in industry is used
Traditional handicraft is in the majority.Wherein most of production technology will be by cyclohexanone oxime Beckmann rearrangement.Either gas phase is still
Liquid phase rearrangement, has more impurity in gained crude caprolactam product, needs to be purified through multi-section before hydrofinishing, such as liquid phase rearrangement
Gained caprolactam need to be also needed by processes such as distillation crystallizations by the processes such as benzene extraction, water extraction, vapour phase rearrangement gained.By these
Still there are some chemical properties impurity similar to caprolactam or the close impurity of boiling point or pair in the caprolactam of purge process
Product is difficult to remove.These impurity can influence permanganate number (the abbreviation PM values, unit second of caprolactam；PM values are higher, represent
The content of unsaturated impurity is fewer), making the quality of caprolactam reduces, so as to influence the quality of downstream product.Can by hydrogenation
So that unsaturated materials hydrogenation saturation, then by distilling removal, while some accessory substances can also be made to be converted into caprolactam,
Improve the utilization rate of accessory substance.
The Chinese invention patent application of Application No. CN 1272490A discloses the amorphous state with nickel as main active component
The hydrofinishing effect of the caprolactam of alloy catalyst.The composition of amorphous alloy catalyst is Ni, 0- of 50-95wt%
A kind of metal in Co, Cr and Mo of the Fe and 0-10wt% of P, 0-25wt% of Al, 0-25wt% of 30wt%.Normal
It is miscellaneous containing unsaturation under the hydrogenation process conditions of rule (gap tank reactor, fixed bed reactors or magnetically stabilized bed reactor)
PM values after the hexanolactam hydrofining of matter are between 3,000-6,000s.The catalyst process is simple, hydrofinishing effect
Fruit is improved, but because there is active metal skewness, there is that hydrogenation activity is low, and service life is short, and caprolactam
The problems such as hydrogenation rear solution distillation increases energy consumption, therefore, seek a kind of Hydrobon catalyst of more efficient caprolactam
And the hydrofinishing process of caprolactam is highly important.
The content of the invention
In view of this, it is an object of the invention to provide the hydrofinishing that a kind of hydrogenation activity is high, hydrofinishing effect is good
Catalyst and preparation method and its application during hexanolactam hydrofining, the purpose of the present invention is by following skill
Art means are realized：
The invention provides a kind of Hydrobon catalyst, including active material outer surface layer and metal alloy kernel, institute
Active material outer surface layer is stated for spongy loose structure, the metal alloy kernel is compact texture；The hydrofinishing is urged
Agent element composition be Ni, Al, Nb and modified metal element M, wherein, Ni contents be 40-65wt%, Al content is 35-
60wt%, Nb content are 0.1%-2wt%, and modified metal element M content is 0-10wt%.
Hydrobon catalyst of the invention belongs to Raney's nickel catalyst.
Preferably, the Ni contents of the Hydrobon catalyst are 45-60wt%, and Al content is 40-55wt%, Nb contents
It is 0.2-1.8wt%, modified metal element M content is 0-6wt%.
Further, the modified metal M is selected from one or more in V, Cr, Mo, W, Fe or Co element, described modified
Metallic element M contents are 0-6wt%.
The invention also discloses a kind of preparation method of Hydrobon catalyst as described above, including：
Step one：By metal alloy Raw material processing into metal alloy particle；
Step 2：Activation process is carried out to the metal alloy particle using alkali lye；
Step 3：The metal alloy particle in the step one by activation process is washed using cleaning solution, obtains described
Hydrobon catalyst.
Further, the preparation process of metal alloy particle is specifically included in the step one：(1) high-temperature fusion skill is used
Metal alloy raw material is prepared into alloy block by art；(2) alloy block obtains the metal conjunction of required size after crushing and screening
Gold grain.
Further, the element composition of the metal alloy raw material is Ni, Al, Nb and modified metal element M, and wherein Ni contains
It is 30-70wt% to measure, and Al content is 30-70wt%, and Nb contents are 0.1-1.5wt%.
Further, the modified metal M is selected from one or more in V, Cr, Mo, W, Fe or Co element, described modified
Metallic element M contents are 0-10wt%.
Further, the particle size of the metal alloy particle is 0.5-10mm.
Preferably, the particle size of the metal alloy particle is 2-7mm.
Further, the alkali lye in the step 2 is that water of the solid NaOH with electrical conductivity less than 200 μ s/cm is formulated
NaOH solution；Preferably, water of the alkali lye in the step 2 by solid NaOH and electrical conductivity less than 100 μ s/cm prepare and
Come.
Further, the NaOH solution concentration is 0.1-8wt%；The mass space velocity of the NaOH solution is 2-20h-1。
Preferably, the NaOH solution concentration is 0.2-6wt%；The mass space velocity of the NaOH solution is 3-15h-1。
Further, described activating treatment temperature is 10-80 DEG C；The described activation process time is 1-12h.
Preferably, described activating treatment temperature is 15-50 DEG C；The described activation process time is 4-10h.
Further, the activated process of the metal alloy particle in the step 2 enters in fixed bed reactors
OK.
Further, the washing process in the step 3 is specially：The NaOH solution is switched into cleaning solution, is used
Metal alloy particle after being activated in the cleaning solution washing step 2, the wash temperature of the washing process is 10-80
DEG C, it is preferable that wash temperature is 20-60 DEG C, when the pH value of the cleaning solution is 7-9, stops washing；The cleaning solution is to go
Ionized water.
Further, the invention also discloses Hydrobon catalyst as described above in hexanolactam hydrofining mistake
Application in journey, including：Hydrofining reaction is carried out to caprolactam using the Hydrobon catalyst；The caprolactam
It is that hydrogenation reaction is carried out with molten state or caprolactam water solution；The concentration of the caprolactam water solution is more than 80wt%, institute
It is 70-150 DEG C to state the temperature of hydrofining reaction, and the reaction pressure of the hydrofining reaction is 0.1-4MPa, described in oneself
The mass space velocity of acid amides is 0.5-15h-1。
Preferably, the concentration of the caprolactam water solution is more than or equal to 85wt% or is molten state caprolactam, institute
The hydrogenation reaction temperature stated is 80-140 DEG C, and described reaction pressure is 0.3-3MPa, the mass space velocity of described caprolactam
It is 2-10h-1。
Relative to prior art, the beneficial effects of the present invention are：
Hydrobon catalyst of the invention is the addition Nb metals on the basis of existing conventional NiAl alloy epitaxy, makes metal unit
Element is evenly distributed, and while improving activity, improves catalyst service life, using High Caprolactam hydrofinishing, is protecting
While holding product quality, energy consumption is reduced.
Brief description of the drawings
Fig. 1 be caprolactam disclosed in this invention unifining process in reaction time and PM values graph of a relation.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, it should be pointed out that embodiment described below purport
Being easy to the understanding of the present invention, and any restriction effect is not played to the scope of protection of present invention.
Embodiment 1-7 is respectively that different-grain diameter prepares graininess thunder with the metal alloy particle of composition through alkali lye activation process
The preparation process of Buddhist nun's Raney nickel.
Embodiment 1
This example demonstrates that average grain diameter is 3mm, it is Ni to constitute42Al57.5Nb0.5Metal alloy particle through alkali lye activate
Treatment prepares the preparation process of graininess Raney's nickel catalyst.
In a particular embodiment, average grain diameter is accurately weighed for 3mm, composition are Ni42Al57.5Nb0.5Metal alloy
Particle 800g, be placed in internal diameter be 40mm quartz glass tube in, concentration for 1wt% NaOH solution (electrical conductivity of water be 50 μ s/
Cm) flowed into by metal alloy particle bed from the bottom of quartz glass tube with the speed of 6.4L/h and then flowed out from top,
The weight space velocity of NaOH solution is 8h-1.Bed temperature is 40 DEG C, and the activation process time is 6h.With 50 DEG C after alkali lye activation process
Deionized water washed, until washing after solution pH be 7-9.Average group of obtained graininess Raney's nickel catalyst
As Ni46.8Al52.6Nb0.6。
Embodiment 2
This example demonstrates that average grain diameter is 3mm, it is Ni to constitute42Al57.5Nb0.5Metal alloy particle through alkali lye activate
Treatment prepares the preparation process of graininess Raney's nickel catalyst.
In a particular embodiment, graininess Raney's nickel catalyst is carried out according to the method described in embodiment 1
Prepare, except that NaOH solution concentration is 2wt%, the base extraction time is 4h, obtained graininess raney ni catalysis
The average composition of agent is Ni47.1Al52.3Nb0.6。
Embodiment 3
This example demonstrates that average grain diameter is 5mm, it is Ni to constitute44Al55Nb1Metal alloy particle through alkali lye activation process
Prepare the preparation process of graininess Raney's nickel catalyst.
In a particular embodiment, graininess Raney's nickel catalyst is carried out according to the method described in embodiment 1
Prepare, except that alloying pellet average grain diameter is 5mm, alloy composition is Ni for composition44Al55Nb1, the weight of NaOH solution
Air speed is 10h-1, the average composition of obtained graininess Raney's nickel catalyst is Ni49.4Al49.4Nb1.2。
Embodiment 4
This example demonstrates that average grain diameter is 3mm, it is Ni to constitute44Al55Nb1Metal alloy particle through alkali lye activation process
Prepare the preparation process of graininess Raney's nickel catalyst.
In a particular embodiment, graininess Raney's nickel catalyst is carried out according to the method described in embodiment 1
Prepare, except that alloy composition is Ni44Al55Nb1, the weight space velocity of NaOH solution is 7h-1, the alkali lye activation process time
It is 8h, the average composition of obtained graininess Raney's nickel catalyst is Ni49.2Al49.7Nb1.1。
Embodiment 5
This example demonstrates that average grain diameter is 3mm, it is Ni to constitute42Al56Nb1Mo1Modified metal alloying pellet through alkali lye
Activation process prepares the preparation process of graininess Raney's nickel catalyst.
In a particular embodiment, graininess Raney's nickel catalyst is carried out according to the method described in embodiment 1
Prepare, except that alloy composition is Ni42Al56Nb1Mo1, the electrical conductivity for preparing alkali lye water is 20 μ s/cm, at alkali lye activation
The reason time is 8h, and the average composition of obtained graininess Raney's nickel catalyst is Ni48.3Al49.8Nb1.2Mo0.6。
Embodiment 6
This example demonstrates that average grain diameter is 3mm, it is Ni to constitute49Al49Nb0.5Mo1.5Modified metal alloying pellet through alkali
Liquid activation process prepares the preparation process of graininess Raney's nickel catalyst.
In a particular embodiment, graininess Raney's nickel catalyst is carried out according to the method described in embodiment 1
Prepare, except that the original composition of metal alloy particle is Ni49Al49Nb0.5Mo1.5, the concentration of alkali lye is 1.2%, made
The average composition of the graininess Raney's nickel catalyst for obtaining is Ni55.3Al42.8Nb0.6Mo1.3。
Embodiment 7
This example demonstrates that average grain diameter is 3mm, it is Ni to constitute46Al50Nb0.5Fe1.5Cr2Modified metal alloying pellet warp
Alkali lye activation process prepares the preparation process of particulate modified molybdenum Raney's nickel catalyst.
In a particular embodiment, particulate modified molybdenum raney ni catalysis are carried out according to the method described in embodiment 1
The preparation of agent, except that the original composition of modified metal alloying pellet is Ni46Al50Nb0.5Fe1.5Cr2, the weight of NaOH solution
Amount air speed is 10h-1, the average composition of obtained particulate modified molybdenum Raney's nickel catalyst is
Ni51.5Al44.1Nb0.7Fe1.2Cr2.5。
Comparative example 1
This comparative example explanation average grain diameter is 3mm, and it is Ni to constitute44Al56Metal alloy particle through alkali lye activation process system
The preparation process of standby particulate modified molybdenum Raney's nickel catalyst.
In a particular embodiment, particulate modified molybdenum raney ni catalysis are carried out according to the method described in embodiment 1
The preparation of agent, the average composition of obtained particulate modified molybdenum Raney's nickel catalyst is Ni49.3Al50.7。
Comparative example 2
This comparative example explanation average grain diameter is 3mm, and it is Ni to constitute44Al55.5Mo1.5Metal alloy particle through alkali lye activate
Treatment prepares the preparation process of particulate modified molybdenum Raney's nickel catalyst.
In a particular embodiment, particulate modified molybdenum raney ni catalysis are carried out according to the method described in embodiment 6
The preparation of agent, the average composition of obtained particulate modified molybdenum Raney's nickel catalyst is Ni51.4Al48.6Mo1.0。
Based on graininess Raney's nickel catalyst prepared by embodiment 1-7 and comparative example 1-2, using fixed bed reactors to oneself
Lactams carries out hydrofining reaction, detects the PM values of the caprolactam water solution after hydrofinishing to reflect hydrofinishing
Energy.
In specific embodiment, take graininess Raney's nickel catalyst take 40mL be fitted into internal diameter be 25mm pipe in, catalyst
Bed height about 8cm, caprolactam caprolactam crystal is heated and is melted, from fixed-bed tube reactor bottom at 100 DEG C
Injection, hydrogen flowing quantity is 15mL/min, reacting system pressure 1.0MPa, and the mass space velocity of caprolactam is 3-6h-1, obtain oneself
Lactams product specification is shown in Table 1.
In specific embodiment, detect that the PM values of caprolactam are adopted with the following method：3.000g caprolactams are poured into
In 100mL colorimetric cylinders, plus distilled water diluting is to scale, shakes up, and is put into 20.0 DEG C of constant temperature water bath, is added in colorimetric cylinder
The liquor potassic permanganate 1mL of 0.01moL/L, shakes up immediately, while opening stopwatch.When color sample in colorimetric cylinder and standard sample
(take 3.000g top pure grade Co (NO3)·6H2O and 12mg top pure grades K2Cr2O7Water is dissolved in, 1 liter is diluted to, shaken up, take 100mL extremely
In colorimetric cylinder) color it is identical when stop stopwatch, write down consumed time (calculating in seconds), as PM values.
In specific embodiments, used catalyst is catalyst prepared by embodiment 1-7 and comparative example 1-2, hydrogenation
Effect see the table below 1.
Table 1
Wherein, be 100 DEG C when temperature, reaction pressure is as the air speed of 1.0MPa, caprolactam solution is 3.0h-1When, it is false
If by taking embodiment 6 and comparative example 2 as an example, the periodic reaction time of graininess Raney's nickel catalyst can be found in figure with the relation of PM values
Shown in 1.
As shown in Table 1, the graininess Raney's nickel catalyst modified by Nb has activity higher, as shown in Figure 1, this hair
The long-lasting catalytic operation of bright offer, still with greater activity.Compared to the prior art, the graininess thunder that the present invention is used
Buddhist nun's Raney nickel, not only activity is high, and long service life, in fixed bed reactors, High Caprolactam is hydrogenated with
Refining reaction, decontamination effect substantially, reduces caprolactam production energy consumption, production technology and equipments are simple, production operation is convenient,
It is easy to industrialization, has a good application prospect and huge economic benefit.
Description to various implementation methods of the invention above is supplied to those skilled in the art with the purpose for describing.It is not
Be intended to exhaustion or be not intended to limit the invention to single disclosed embodiment.As described above, of the invention various
Substitute and change will be apparent for above-mentioned technology one of ordinary skill in the art.Therefore, although specifically beg for
The implementation method of some alternatives has been discussed, but other embodiment will be apparent, or those skilled in the art are relative
Easily draw.It is contemplated that including the of the invention all replacements, modification and the change that had discussed herein, and fall
Other embodiment in the spirit and scope of above-mentioned application.
Although depicting the present invention by implementation method, it will be appreciated by the skilled addressee that the present invention has many deformations
With change without deviating from spirit of the invention, it is desirable to which appended claim includes these deformations and changes without deviating from the present invention
Spirit.
Claims (15)
1. Hydrobon catalyst, it is characterised in that including active material outer surface layer and metal alloy kernel, the active matter
Matter outer surface layer is spongy loose structure, and the metal alloy kernel is compact texture；The unit of the Hydrobon catalyst
Element composition be Ni, Al, Nb and modified metal element M, wherein, Ni contents be 40-65wt%, Al content is 35-60wt%, and Nb contains
It is 0.1%-2wt% to measure, and modified metal element M content is 0-10wt%.
2. Hydrobon catalyst as claimed in claim 1, it is characterised in that the Ni contents of the Hydrobon catalyst are
45-60wt%, Al content is 40-55wt%, and Nb contents are 0.2-1.8wt%, and modified metal element M content is 0-6wt%.
3. the Hydrobon catalyst as described in any one of claim 2, it is characterised in that the modified metal M be selected from V, Cr,
One or more in Mo, W, Fe or Co element, the modified metal element M content is 0-6wt%.
4. the preparation method of the Hydrobon catalyst as described in claim any one of 1-3, including：
Step one：By metal alloy Raw material processing into metal alloy particle；
Step 2：Activation process is carried out to the metal alloy particle using alkali lye；
Step 3：The metal alloy particle in the step one by activation process is washed using cleaning solution, the hydrogenation is obtained
Catalyst for refining.
5. the preparation method of Hydrobon catalyst as claimed in claim 4, it is characterised in that metal is closed in the step one
The preparation process of gold grain includes：(1) high-temperature fusion technology is used by metal alloy Raw material processing into alloy block；(2) conjunction
Gold bullion obtains the metal alloy particle of required size after crushing and screening.
6. the preparation method of Hydrobon catalyst as claimed in claim 4, the element composition of the metal alloy compositions is
Ni, Al, Nb and modified metal element M, wherein Ni contents are 30-70wt%, and Al content is 30-70wt%, and Nb contents are 0.1-
1.5wt%, the modified metal element M is selected from one or more in V B, VI B or VIII race's element, the modified metal element
M contents are 0-10wt%.
7. the preparation method of Hydrobon catalyst as claimed in claim 6, it is characterised in that the modified metal M is selected from
One or more in V, Cr, Mo, W, Fe or Co element, the modified metal element M content is 0-5wt%.
8. the preparation method of Hydrobon catalyst as claimed in claim 4, it is characterised in that the metal alloy particle
Particle size is 0.5-10mm.
9. the preparation method of Hydrobon catalyst as claimed in claim 4, it is characterised in that described alkali lye is solid
The NaOH solution that water of the NaOH with electrical conductivity less than 200 μ s/cm is formulated.
10. the preparation method of Hydrobon catalyst as claimed in claim 9, it is characterised in that the NaOH solution concentration
It is 0.1-8wt%；The mass space velocity of the NaOH solution is 2-20h-1。
The preparation method of 11. Hydrobon catalysts as claimed in claim 4, it is characterised in that described activation process temperature
Spend is 10-80 DEG C；The described activation process time is 1-12h.
The preparation method of 12. Hydrobon catalysts as claimed in claim 4, it is characterised in that metal in the step 2
The activated process of alloying pellet is carried out in fixed bed reactors.
The preparation method of 13. Hydrobon catalysts as claimed in claim 4, it is characterised in that washing in the step 3
The process of washing is specially：The NaOH solution is switched into cleaning solution, after being activated in the cleaning solution washing step one
Metal alloy particle, the wash temperature of the washing process is 10-80 DEG C, when the pH value of the cleaning solution is 7-9, is stopped
Washing；The cleaning solution is deionized water.
Application of 14. Hydrobon catalyst as described in claim any one of 1-3 during hexanolactam hydrofining,
Including：Hydrofining reaction is carried out to caprolactam using the Hydrobon catalyst；The caprolactam is with molten state
Or caprolactam water solution carries out hydrogenation reaction；The concentration of the caprolactam water solution is more than 80wt%, the hydrofinishing
The temperature of reaction is 70-150 DEG C, and the reaction pressure of the hydrofining reaction is 0.1-4MPa, the quality of the caprolactam
Air speed is 0.5-15h-1。
Application of 15. Hydrobon catalysts as claimed in claim 14 during hexanolactam hydrofining, its feature
It is that the concentration of the caprolactam water solution is more than 85wt% or is molten state, and described hydrogenation reaction temperature is 80-140
DEG C, described reaction pressure is 0.3-3MPa, and the mass space velocity of described caprolactam is 2-10h-1。
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Cited By (2)
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| CN110871083A (en) * | 2019-12-03 | 2020-03-10 | 中国科学院青岛生物能源与过程研究所 | Bulk hydrodeoxygenation catalyst and preparation method thereof |
| CN112871184A (en) * | 2021-02-09 | 2021-06-01 | 大连理工大学 | Catalyst for preparing 1, 4-butanediol by fixed bed hydrogenation of 1, 4-butynediol and preparation method and application thereof |
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| CN106693992B (en) | 2019-06-25 |
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