CN109985628A - Hydrotalcite composite transition metal catalyst faces the purposes in hydrogen ammonolysis reaction for aldehydes or ketone compounds - Google Patents
Hydrotalcite composite transition metal catalyst faces the purposes in hydrogen ammonolysis reaction for aldehydes or ketone compounds Download PDFInfo
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- CN109985628A CN109985628A CN201810001682.6A CN201810001682A CN109985628A CN 109985628 A CN109985628 A CN 109985628A CN 201810001682 A CN201810001682 A CN 201810001682A CN 109985628 A CN109985628 A CN 109985628A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
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Abstract
A kind of hydrotalcite composite catalyst is used for the purposes of aldehydes or ketone compounds faced hydrogen ammonolysis and prepare aminated compounds.The present invention uses hydrotalcite or houghite composite transition metal simple substance to make active component as catalyst, is catalyzed aldehydes or ketone compounds in a hydrogen atmosphere and ammonia carries out ammonolysis reaction, aminated compounds is made.And by adjusting the conversion conditions such as reaction temperature, residence time and catalyst amount, the high conversion and target product aminated compounds of Lai Shixian aldehydes or ketone compounds it is highly selective.The features such as catalyst of the invention is applied to the reaction of aldehydes or ketone compounds faced hydrogen ammonolysis and prepare aminated compounds, has catalyst cheap, target product yield height and good catalyst stability.
Description
Technical field
The present invention relates to a kind of hydrotalcite or the composite catalyst of houghite composite transition metal simple substance active component with
And it faces the highly selective method for preparing aminated compounds of hydrogen ammonolysis for aldehydes or ketone compounds.
Technical background
Aminated compounds is a kind of very important organic compound, is widely present in the Nature, such as hormone, life
Alkaloids and antibiotic etc.；Also medicinal activity substance, pesticide, household chemicals and petrochemical industry important source material and reaction
Intermediate feed, for example, as solvent, medicinal activity intermediate, resin raw material, additive, disinfectant, rubber stabilizer, corruption
Corrosion inhibitor, detergent etc..For example, cyclohexylamine is a kind of important Organic Chemicals and fine chemical product intermediate, it
It is widely used in rubber chemicals, food additives, anti-corrosion, papermaking, plastic processing and textile industry.Mainly have in the world so far
Six kinds of cyclohexylamine preparation methods, i.e. aniline catalytic hydrogenation non-pressure process and pressurization, nitrocyclohexane reduction method, chlorocyclohexane are urged
Change ammonolysis process, the direct ammoniation process of cyclohexene, cyclohexanone catalytic ammoniation method, hexamethylene alcohol catalysis ammonolysis process.In view of raw material price,
Source and simple process, domestic industry production cyclohexylamine mainly use aniline catalytic hydrogenation pressurization, use in the method
Catalyst can be divided into cobalt system, ruthenium system, nickel system and palladium system with chief active element classification.Cobalt series catalyst Reporting is richer
Richness, the cobalt Zr catalyst that Japan Patent 7424905 is reported, the molar fraction of cyclohexylamine up to 97%, report by Poland Patent 128708
Road is a kind of using alkaline earth oxide as the Co catalysts of carrier, also there is more good effect.Using cobalt as catalyst in document,
240 DEG C of temperature, 14.7~19.6MPa of pressure, the molar ratio of aniline and hydrogen is 1:10,0.4~0.7h of air speed-1, liquid-phase hydrogenatin,
80~89% cyclohexylamine, less generation dicyclohexyl amine can be obtained.The air speed of this method reactor is low, and the cyclohexylamine purity of production is not
It is high, it is difficult to meet the needs of production and application, secondly using technique that nitrobenzene is raw material production aniline there are biggish environmental pollution,
The selectivity of the conversion per pass of aniline and cyclohexylamine is all up for improving simultaneously, and reaction pressure is high, and there are certain peaces
Full problem.In addition, aniline catalytic hydrogenation non-pressure process utilization ratio of device is low, energy consumption is big, and product yield (in terms of aniline) also only has
90%, constrain its extensive use and popularization industrially.
Cyclohexanone source is fairly simple both at home and abroad at present, and the production technology of research and development Cyclohexanone Production cyclohexylamine has well
Market prospects.Xing Xiaodong et al. has studied using Ni- diatomite as catalyst, the method for preparing cyclohexylamine by cyclohexanone,
Reactive hydrogen pressure is 8.0-9.0MPa, and in 353-393K, cyclohexylamine yield is 83% for reaction temperature control.Et al.
(Applied Catalysis A:General, 197 (2000) 229-238) uses Ni/Al2O3/SiO2(44wt%Ni) conduct
Catalyst has studied the method that cyclohexanone prepares cyclohexylamine, obtains at 200 DEG C of reaction temperature 100% conversion ratio and 80%
Cyclohexylamine selectivity.The grade of Ruan Ji discloses a kind of catalyst for preparing fatty amine and technique in CN1044689C patent,
It is characterized in that the catalyst uses aluminium oxide made from high-temperature roasting to constitute for carrier and nickel, copper, chromium active component, each group sub-prime
Measure percentage composition are as follows: nickel 1.5~20%, copper 1.5~20%, chromium 0.05~5%；When using the catalyst preparation fatty amine, packet
Include catalyst pretreatment, aminating reaction；Aminating reaction condition is: 230~280 DEG C of temperature, 0.1~3.0MPa of pressure,
Air speed (volume) 0.1~5.0h-1, the molar ratio of liquefied ammonia and raw material is 0.5~10.0.
In addition, aromatic primary amine is a kind of important chemical intermediate in industrial production, benzene methanamine and m-xylene diamine are them
In most important two kinds.Benzene methanamine is also known as Bian amine, can be with phenol, formic acid, p-methyl phenol etc. with stronger alkalinity
Interaction generates addition product；It is widely used in medicine, chemical reagent, dyestuff, synthetic resin, two in modern industrial production
In terms of aoxidizing absorbent carbon, corrosion inhibitor and agrochemical.The main Bian chlorine addition process of the synthetic method of benzene methanamine, Bian chlorine ammonolysis
Method, benzaldehyde ammoniation process and benzene first eyeball hydrogenation method etc..What wherein technique was more mature is that Bian chlorine addition process prepares benzene methanamine, however is somebody's turn to do
Process requires height to consersion unit, and processing step is cumbersome, and benzene methanamine yield is only 60% or so.
In conclusion it is existing by aldehydes or ketone compounds prepare aminated compounds catalyst there are catalytic effects not
It is ideal or reaction condition is required it is harsh, therefore find a kind of catalytic activity is high, selectivity is high, the service life is long, it is relative moderate by
The catalyst that aldehydes or ketone compounds prepare aminated compounds is to develop aldehydes or ketone compounds to face hydrogen ammonolysis highly selective
Prepare aminated compounds research direction.
Summary of the invention
The object of the present invention is to provide the compound of a kind of hydrotalcite or houghite composite transition metal simple substance active component
Catalyst.
According to the first embodiment of the present invention, hydrotalcite composite catalyst is provided for aldehydes in a hydrogen atmosphere
Or the purposes in the ammonolysis reaction between ketone compounds and ammonia, it is characterised in that the hydrotalcite composite catalyst is by neatly
Stone or houghite composite transition metal simple substance active component are formed by, and wherein transition metal simple substance active component includes main work
Property component and help active component, the main active component be selected from the periodic table of elements in group viii b transition metal one
Kind or it is a variety of, it is described that help active component be one of I B~VIIB group 4 transition metal or more in the periodic table of elements
Kind.
Preferably, the main active component accounts for 0.5~50wt% of composite catalyst gross mass, preferably 1-
45wt%, more preferable 5~40wt%, more preferable 10~35wt%；Help active component account for composite catalyst gross mass 0.01~
30wt%, preferably 0.1-25wt%, more preferable 1~20wt%, more preferable 3~15wt%.
It is preferred that the main active component is selected from one of ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), nickel (Ni) or more
Kind and described active component is helped to be selected from one of copper (Cu), silver-colored (Ag), golden (Au), zirconium (Zr), tungsten (W) or a variety of.
More specifically, the purposes is hydrotalcite composite catalyst facing in hydrogen ammonolysis reaction for cyclohexanone and ammonia
Prepare the catalysis ammonia of the purposes or hydrotalcite composite catalyst of cyclohexylamine for the mixture and ammonia of cyclohexanol and cyclohexanone
Solution reaction prepares the purposes of cyclohexylamine.
In such use, it is preferable that the hydrotalcite composite catalyst a kind of is prepared by what is included the following steps
It is prepared by method:
1) be co-precipitated: by divalent metal salt, trivalent metal salt, main activity component metal salt and help activity component metal salt with
And alkaline coprecipitator is dissolved in deionized water and is made into mixed liquor, will be formed by mixed liquor and is heated under stiring (such as in 35-
8~15h is heated at 150 DEG C) so that all metal ions are co-precipitated, control pH value be lower than 7 (preferably 3.5-7, more preferably
4-6, more preferable 4.5-5.5, such as 5 or so), obtain slurries, then gained slurries cooling (such as be cooled to 10~50 DEG C,
It is preferred that being cooled to 20~40 DEG C of temperature) after thermostatic crystallization (such as 12~for 24 hours), the reaction solution after crystallization was carried out later
Filter, washing and drying, are then optionally ground, obtain hydrotalcite or houghite base complex；The wherein divalent gold
Belong to salt and the trivalent metal salt is to form hydrotalcite or the required divalent metal salt of houghite and three respectively
Valence metal salt (is preferably all water soluble salt), and main activity component metal salt is the group viii b transition in the periodic table of elements
The salt (preferably water soluble salt) of one of metal or various metals, it is described help activity component metal salt be selected from element week
The water soluble salt (preferably water soluble salt) of one of I B~VIIB group 4 transition metal or various metals in phase table；
2) hydrotalcite of step 1) preparation or houghite base complex are roasted, obtains hydrotalcite or houghite base is multiple
Close oxide；
3) hydrotalcite or houghite the base composite oxidate reduction obtained step 2), obtains hydrotalcite or houghite
Base composite transition metal simple substance catalyst, that is, composite catalyst.
Generally, alkaline coprecipitator is, for example: urea, sodium hydroxide and sodium carbonate, alternatively, ammonia or ammonium hydroxide and carbonic acid
Sodium, etc..The effect of sodium carbonate therein is to provide carbanion (CO required for forming hydrotalcite or houghite3 2+)。
Salt (preferably water soluble salt) described herein is, for example, nitrate, acetate, sulfate or chloride.
In order to form hydrotalcite or the required divalent metal salt of houghite is divalent as known in the art gold
Belong to salt (preferably water soluble salt), is e.g. selected from Mg2+, Ni2+, Co2+, Zn2+Or Cu2+In divalent metal salt
(such as nitrate, acetate, sulfate or chloride).
In order to form hydrotalcite or the required trivalent metal salt of houghite is trivalent as known in the art gold
Belong to salt (preferably water soluble salt), is e.g. selected from Al3+, Cr3+, Fe3+Or Sc3+In trivalent metal cation salt (such as
Nitrate, acetate, sulfate or chloride, more preferably water-soluble salt).
Metal in divalent metal salt or trivalent metal salt can with above-mentioned main activity component metal salt or help active component
Metal in metal salt is identical or different.
Preferably, in the above-mentioned methods, the temperature that the heating co-precipitation is carried out in step 1) is 35-150 DEG C, preferably
It is 50-120 DEG C, more preferable 80~110 DEG C；It is preferred that temperature dry described in step 1) is 100-130 DEG C, preferably 105-
125 DEG C, more preferable 110~120 DEG C.
Preferably, in the above-mentioned methods, in step 2): the temperature of roasting be 300-900 DEG C, preferably 400-800 DEG C,
More preferably 500-700 DEG C；And/or the time of roasting is 0.5-15h, preferably 1-10h, more preferably 1.5-8h.It is preferred that
The roasting is carried out using Muffle furnace.
Preferably, in the step 3) of the above method, hydrotalcite or houghite base composite oxygen that step 2) is obtained
Compound is restored using hydrogen.It is preferred that the temperature of reduction reaction be 200-800 DEG C, preferably 300-700 DEG C, more preferably
400-600℃.It is preferred that the time of reduction reaction is 1-15h, preferably 2-10h, more preferably 3-8h.
Generally, in step 1), divalent metal salt, trivalent metal salt, activity component metal salt and activity component metal is helped
The molar ratio of salt is 2-4:0.5-2.0:0.1-2:0.05-1.3, preferably 2-4:0.7-1.5:0.2-1.6:0.08-1.0, such as
3:1:0.3:0.1。
Generally, in step 1), alkaline coprecipitator (for example, urea, sodium hydroxide and sodium carbonate, alternatively, ammonia or ammonia
Water and sodium carbonate) dosage be sufficient to make all metal ions in mixed liquor to be co-precipitated；Preferably, alkaline coprecipitator
1.1-5 times for the integral molar quantity of all metal ions in mixed liquor of dosage, preferably 1.2-4 times, more preferably
1.3-3 times, such as 2 or 2.5 times.
According to the second embodiment of the present invention, it also provides a kind of in a hydrogen atmosphere by aldehydes or ketone compounds
The method for preparing aminated compounds with the catalysis ammonolysis reaction of ammonia, this method comprises: in the presence of hydrotalcite composite catalyst
It is mixed in the reactor in a hydrogen atmosphere by aldehydes or ketone compounds with ammonia and carries out ammonolysis reaction to which amine be made
Class compound,
It is characterized by: the hydrotalcite composite catalyst is living by hydrotalcite or houghite composite transition metal simple substance
Property component be formed by, wherein transition metal simple substance active component includes main active component and helping active component, the main activity
Component is one of group viii b transition metal or a variety of in the periodic table of elements, and described to help active component be to be selected from
One of I B~VIIB group 4 transition metal or a variety of in the periodic table of elements.
Preferably, the main active component accounts for 0.5~50wt% of composite catalyst gross mass, preferably 1-
45wt%, more preferable 5~40wt%, more preferable 10~35wt%；Help active component account for composite catalyst gross mass 0.01~
30wt%, preferably 0.1-25wt%, more preferable 1~20wt%, more preferable 3~15wt%.
It is preferred that the main active component is selected from one of ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), nickel (Ni) or more
Kind and described active component is helped to be selected from one of copper (Cu), silver-colored (Ag), golden (Au), zirconium (Zr), tungsten (W) or a variety of.
It is preferred that the reactor is pressure autoclave type reactor, fluidized bed or solid in the preparation method of aminated compounds
One of fixed bed reactor；Preferred reactor is fixed bed reactors.
It is preferred that in the preparation method of aminated compounds, the molar ratio of aldehydes or ketone compounds and ammonia is 0.01~5:
1, preferably 0.03~4:1, more preferable 0.05~3:1, more preferable 0.07~2.5:1.
It is further preferred that reaction temperature is 50~400 DEG C, preferably 100 DEG C~300 DEG C, more preferably 150 DEG C~200 DEG C；
And/or
It is further preferred that the pressure of reaction is normal pressure~5MPa, preferably normal pressure~4MPa, more preferably normal pressure~3MPa.
Equally, the hydrotalcite composite catalyst is prepared by a kind of above-described preparation method.
In this application, " optionally " indicate carry out or without.
Present inventor surprisingly, it is found that, above-mentioned composite catalyst or by the above method prepare catalyst
Face hydrogen ammonolysis reaction particularly suitable for aldehydes or ketone compounds and ammonia, conversion ratio and selectivity are all ideal.Therefore,
According to an embodiment of the invention, provide above-mentioned composite catalyst or by above method preparation catalyst for aldehydes or
The purposes of ketone compounds and ammonia faced in hydrogen ammonolysis reaction.It is preferred that the composite catalyst is used for cyclohexanone, hexandial and benzene first
Purposes in the catalytic hydroprocessing ammonolysis reaction of aldehyde and ammonia.
According to an embodiment of the invention, providing through the catalytic hydroprocessing ammonolysis reaction of cyclohexanone and ammonia to prepare hexamethylene
The method of amine, this method comprises: being mixed in the reactor by cyclohexanone with ammonia in the presence of composite catalyst and carrying out ammonia
Solution reaction is to be made cyclohexylamine, wherein composite catalyst is used as, using above-mentioned composite catalyst or use by above method system
Standby composite catalyst.
It is preferred that the reactor is one of pressure autoclave type reactor, fluidized bed or fixed bed reactors；More preferably
Reactor is fixed bed reactors；
It is preferred that the molar ratio of cyclohexanone and ammonia be 0.01~5:1, preferably 0.03~4:1, more preferable 0.05~3:1, more
It is preferred that 0.07~2.5:1.
It is preferred that prepare in the method for cyclohexylamine, reaction temperature is 50~400 DEG C, preferably 100 DEG C~300 DEG C, more preferably
It is 150 DEG C~200 DEG C.
It is preferred that prepare in the method for cyclohexylamine, the pressure of reaction is normal pressure~5MPa, preferably normal pressure~4MPa, more excellent
It is selected as normal pressure~3MPa.
Catalyst of the invention is cheap, and has very high catalytic activity, selectivity, stability.
In addition, the technical solution of the present invention is as follows:
A kind of aldehydes or ketone compounds face hydrogen ammonolysis catalyst, using hydrotalcite or houghite composite transition metal
Simple substance active component is catalyst, which includes main active component and help active component.Described helps active component to be selected from
One or more of I B~VIIB group 4 transition metal in the periodic table of elements, preferably copper (Cu), silver-colored (Ag)), gold (Au), zirconium
(Zr), one or more of tungsten (W) etc.；Main active component group viii b transition metal in the periodic table of elements
One or more of, preferably one or more of ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), nickel (Ni) etc.；The master
Active component accounts for the 1.0~50% of catalyst gross mass, it is described help active component account for catalyst gross mass 0.01~
10.0%.Preparation method includes the following steps:
(1) using coprecipitation preparation containing the main hydrotalcite or houghite base complex for helping active component, co-precipitation
Temperature be 30-120 DEG C, preferably 80~110 DEG C；
(2) above-mentioned hydrotalcite or houghite base complex are placed in Muffle furnace, it is small in 400~800 DEG C of roastings 1~10
When, preferably 500~700 DEG C, obtain hydrotalcite or houghite base composite oxidate；
(3) by hydrotalcite or houghite base composite oxidate in 300~700 DEG C of hydrogen reductase 12~10 hour, it is excellent
400~600 DEG C are selected, hydrotalcite or houghite based composite catalyst, i.e. aldehydes or the catalysis of ketone compounds ammonolysis can be obtained
Agent.
Face hydrogen ammonolysis for aldehydes or ketone compounds using catalyst obtained by the above method and prepare aminated compounds
Reaction, specifically:
Under the conditions of 100 DEG C~300 DEG C, normal pressure~6MPa, by aldehydes or ketone compounds with ammonolysis catalyst anti-
It answers and carries out hybrid reaction in device, obtain target product aminated compounds.
Further, the reactor can be pressure autoclave type reactor, fluidized bed or fixed bed reactors, preferably fix
Bed reactor；
Reaction temperature is 100 DEG C~300 DEG C, preferably 150 DEG C~200 DEG C；
Pressure is normal pressure~6MPa, preferably normal pressure~2MPa；
The aldehydes or ketone compounds of reaction and the molar ratio of ammonia are 0.01~2, preferably 0.05~1.
Advantageous effects of the invention
Catalyst of the invention is made the compound of active component and is urged using hydrotalcite or houghite composite transition metal simple substance
Agent, preparation method simple process, for the of less demanding of equipment, short preparation period, the catalyst of synthesis is particularly suitable for using
In the reaction of cyclohexanone faced hydrogen ammonolysis and prepare cyclohexylamine, yclohexanone conversion ratio is up to 100%, the selectivity of cyclohexylamine
95%, catalyst stability and catalytic activity were high, long service life, up to 300 hours or more；With existing synthetic method gained
Catalyst is compared, and catalyst stability obtained by this method is significantly improved, and reaction condition is more mild.
Specific embodiment
The present invention is described in further details below by specific embodiment, rather than limiting the invention.
Preparation example 1
At 90-110 DEG C, prepared using urea coprecipitation method containing main active component nickel and the neatly for helping active ingredient copper
Stone.Weigh magnesium nitrate (Mg (NO respectively first3)2·6H2O, 76.92g), aluminum nitrate (Al (NO3)3·9H2O, 37.52g), nitric acid
Nickel (Ni (NO3)2·6H2O, 8.6g) and copper nitrate (Cu (NO3)2·3H2O, 2.6g) (metal cation is in molar ratio=3:1:
0.3:0.1) and 216.22g urea, it is dissolved in 350mL deionized water and is made into mixed liquor, by mixed liquor in 95 in three-necked flask
Heating stirring 10h at DEG C, control pH value is 5 or so, gained slurries thermostatic crystallization 18h at 25 DEG C, by the reaction solution after crystallization
It is filtered, washed, it is then 12 hours dry at 110 DEG C, it obtains containing main active component nickel and the hydrotalcite for helping active ingredient copper.It will
Hydrotalcite obtained is placed in Muffle furnace, is roasted 2 hours at 600 DEG C, is obtained the hydrotalcite composite oxides containing copper and mickel.It will
The composite oxides restore 8 hours in 550 DEG C of hydrogen stream, obtain catalyst A, the matter of main active component nickel in catalyst A
Amount percentage composition is 9wt%, help active ingredient copper mass percentage be 3wt% (both with respect to catalyst gross mass, under
Together).
Compare preparation example 1
At 90-110 DEG C, the hydrotalcite containing only main active component nickel is prepared using urea coprecipitation method.Claim respectively first
Take magnesium nitrate (Mg (NO3)2·6H2O, 76.92g), aluminum nitrate (Al (NO3)3·9H2O, 37.52g) and nickel nitrate (Ni (NO3)2·
6H2O, 11.67g) (metal cation is in molar ratio=3:1:0.4) and 216.22g urea, it is dissolved in 350mL deionized water and matches
At mixed liquor, by mixed liquor, heating stirring 10h, control pH value are 5 at 95 DEG C in three-necked flask, and gained slurries are at 25 DEG C
Reaction solution after crystallization is filtered, washed by thermostatic crystallization 18h, then 12 hours dry at 110 DEG C, is obtained containing only main activity
The hydrotalcite of component nickel.Hydrotalcite obtained is placed in Muffle furnace, is roasted 2 hours at 600 DEG C, is obtained containing containing only main active group
Divide the hydrotalcite composite oxides of nickel.The catalyst is restored 8 hours in 550 DEG C of hydrogen stream, catalyst B is obtained, urges
The mass percentage of nickel is 12wt% in agent B.
Compare preparation example 2
At 90-110 DEG C, prepared using urea coprecipitation method containing only the hydrotalcite for helping active ingredient copper.Claim respectively first
Take magnesium nitrate (Mg (NO3)2·6H2O, 76.92g), aluminum nitrate (Al (NO3)3·9H2O, 37.52g) and copper nitrate (Cu (NO3)2·
3H2O, 7.5g) (metal cation is in molar ratio=3:1:0.4) and 216.22g urea, it is dissolved in 350mL deionized water and is made into
Mixed liquor, by mixed liquor, heating stirring 10h, control pH value are 5 or so at 95 DEG C in three-necked flask, and gained slurries are at 25 DEG C
Lower thermostatic crystallization 18h, the reaction solution after crystallization is filtered, washed, and then dry 12 hours at 110 DEG C, is obtained containing only helping work
The hydrotalcite of property component copper.Hydrotalcite obtained is placed in Muffle furnace, is roasted 2 hours at 600 DEG C, is obtained containing containing only helping activity
The hydrotalcite composite oxides of component copper.The catalyst is restored 8 hours in 550 DEG C of hydrogen stream, obtains catalyst C,
The mass percentage of copper is 12wt% in catalyst C.
Compare preparation example 3
At 90-110 DEG C, using the not nickeliferous hydrotalcite with copper of urea coprecipitation method preparation.Weigh nitric acid respectively first
Magnesium (Mg (NO3)2·6H2O, 76.92g) and aluminum nitrate (Al (NO3)3·9H2O, 37.52g) (metal cation is in molar ratio=3:
1) and 216.22g urea, be dissolved in 350mL deionized water and be made into mixed liquor, by mixed liquor in three-necked flask at 95 DEG C plus
Thermal agitation 10h, control pH value are 5, gained slurries thermostatic crystallization 18h at 25 DEG C of left and right, and the reaction solution after crystallization is filtered, is washed
It washs, it is then 12 hours dry at 110 DEG C, obtain not nickeliferous and copper hydrotalcite.Hydrotalcite obtained is placed in Muffle furnace,
It is roasted 2 hours at 600 DEG C, obtains nickeliferous and copper hydrotalcite composite oxides.Hydrogen by the catalyst at 550 DEG C
It is restored 8 hours in stream, obtains catalyst D, be free of copper and mickel, as individual hydrotalcite substance in catalyst D.
Compare preparation example 4
At 90-110 DEG C, using the not nickeliferous houghite with copper of urea coprecipitation method preparation.Weigh nitre respectively first
Sour magnesium (Mg (NO3)2·6H2O, 76.92g) and ferric nitrate (Fe (NO3)3·9H2O, 40.40g) (metal cation in molar ratio=
3:1) and 216.22g urea, it is dissolved in 350mL deionized water and is made into mixed liquor, by mixed liquor in three-necked flask at 95 DEG C
Heating stirring 10h, control pH value are 5 or so, gained slurries thermostatic crystallization 18h at 25 DEG C, the reaction solution after crystallization is filtered,
Washing, it is then 12 hours dry at 110 DEG C, obtain not nickeliferous and copper houghite.Houghite obtained is placed in horse
It not in furnace, is roasted 2 hours at 600 DEG C, obtains nickeliferous and copper houghite base composite oxidate.The catalyst is existed
It is restored 8 hours in 550 DEG C of hydrogen stream, obtains catalyst E, be free of copper and mickel in catalyst E, that is, individual houghite object
Matter.
Compare preparation example 5
At 90-110 DEG C, prepared using urea coprecipitation method containing main active component nickel and the neatly for helping active component silver
Stone.Weigh magnesium nitrate (Mg (NO respectively first3)2·6H2O, 76.92g), aluminum nitrate (Al (NO3)3·9H2O, 37.52g), nitric acid
Nickel (Ni (NO3)2·6H2O, 8.6g) and silver nitrate (AgNO3, 0.85g) and (metal cation is in molar ratio=3:1:0.3:0.05)
And 216.22g urea, it is dissolved in 350mL deionized water and is made into mixed liquor, mixed liquor is heated at 95 DEG C in three-necked flask
10h is stirred, control pH value is 5 or so, gained slurries thermostatic crystallization 18h at 25 DEG C, and the reaction solution after crystallization is filtered, is washed
It washs, it is then 12 hours dry at 110 DEG C, it obtains containing main active component nickel and the hydrotalcite for helping active component silver.It will be obtained
Hydrotalcite is placed in Muffle furnace, is roasted 2 hours, is obtained containing main active component nickel and the hydrotalcite for helping active component silver at 600 DEG C
Base composite oxidate.The composite oxides are restored 8 hours in 550 DEG C of hydrogen stream, obtain catalyst F, master in catalyst F
The mass percentage of active component nickel is 9%, and helping the mass percentage of active component silver is 1.5wt%.
Compare preparation example 6
At 90-110 DEG C, prepared using urea coprecipitation method containing main active component nickel and the neatly for helping active component zirconium
Stone.Weigh magnesium nitrate (Mg (NO respectively first3)2·6H2O, 76.92g), aluminum nitrate (Al (NO3)3·9H2O, 37.52g), nitric acid
Nickel (Ni (NO3)2·6H2O, 8.6g) and zirconium nitrate (Zr (NO3)4·5H2O, 2.15g) (metal cation is in molar ratio=3:1:
0.3:0.05) and 216.22g urea, it is dissolved in 350mL deionized water and is made into mixed liquor, by mixed liquor in 95 in three-necked flask
Heating stirring 10h at DEG C, control pH value is 5 or so, gained slurries thermostatic crystallization 18h at 25 DEG C, by the reaction solution after crystallization
It is filtered, washed, it is then 12 hours dry at 110 DEG C, it obtains containing main active component nickel and the hydrotalcite for helping active component zirconium.It will
Hydrotalcite obtained is placed in Muffle furnace, is roasted 2 hours at 600 DEG C, and nickeliferous and zirconium houghite base composite oxidate is obtained.
The composite oxides are restored 8 hours in 550 DEG C of hydrogen stream, obtain catalyst G, main active component nickel in catalyst G
Mass percentage is 9%, and helping the mass percentage of active component zirconium is 1.5wt%.
Compare preparation example 7
At 90-110 DEG C, prepared using urea coprecipitation method containing main active component ruthenium and the neatly for helping active ingredient copper
Stone.Specially weigh magnesium nitrate (Mg (NO respectively first according to molar ratio=3:1:0.01:0.013)2·6H2O, 76.92g), nitre
Sour aluminium (Al (NO3)3·9H2O, 37.52g), nitric acid ruthenium (RuCl3·3H2O, 0.26g) and copper nitrate (Cu (NO3)2·3H2O,
0.19g) (metal cation is in molar ratio=3:1:0.3:0.01:0.01) and 216.22g urea, are dissolved in 350mL deionization
Water is made into mixed liquor, and by mixed liquor, heating stirring 10h, control pH value are 5 or so at 95 DEG C in three-necked flask, gained slurries
The thermostatic crystallization 18h at 25 DEG C, the reaction solution after crystallization is filtered, washed, then 12 hours dry at 110 DEG C, is contained
Main active component ruthenium and the hydrotalcite for helping active ingredient copper.Hydrotalcite obtained is placed in Muffle furnace, roasts 2 at 600 DEG C
Hour, obtain the houghite base composite oxidate containing ruthenium and copper.It is small that the composite oxides are restored to 8 in 550 DEG C of hydrogen stream
When, catalyst H is obtained, the mass percentage of main active component ruthenium is 1wt% in catalyst H, helps the quality of active ingredient copper
Percentage composition is 0.5wt%.
Compare preparation example 8
At 90-110 DEG C, prepared using urea coprecipitation method containing main active component rhodium and the neatly for helping active ingredient copper
Stone.Magnesium nitrate (Mg (NO is weighed respectively3)2·6H2O, 76.92g), aluminum nitrate (Al (NO3)3·9H2O, 37.52g), rhodium nitrate
(RhCl3·3H2O, 0.26g) and copper nitrate (Cu (NO3)2·3H2O, 0.19g) (metal cation is in molar ratio=3:1:0.3:
0.01:0.01) and 216.22g urea, be dissolved in 350mL deionized water and be made into mixed liquor, by mixed liquor in three-necked flask in
Heating stirring 10h at 95 DEG C, control pH value is 5 or so, gained slurries thermostatic crystallization 18h at 25 DEG C, by the reaction after crystallization
Liquid is filtered, washed, then 12 hours dry at 110 DEG C, is obtained containing main active component rhodium and the hydrotalcite for helping active ingredient copper.
Hydrotalcite obtained is placed in Muffle furnace, is roasted 2 hours at 600 DEG C, the houghite base combined oxidation of rhodium-containing and copper is obtained
Object.The composite oxides are restored 8 hours in 550 DEG C of hydrogen stream, obtain catalyst I, main active component rhodium in catalyst I
Mass percentage be 1wt%, help active ingredient copper mass percentage be 0.5wt%.
Application Example
The hydrogen ammonolysis of facing for being used for cyclohexanone, hexandial and benzaldehyde of catalyst A-I obtained by above-described embodiment is prepared into hexamethylene
In the reaction of amine, hexamethylene diamine and benzene methanamine, its reactivity worth is evaluated.
Embodiment 1
In fixed bed device, 6 centimetres of above-mentioned gained A catalyst of height (1.2g) are packed into, are charging with cyclohexanone, 170
DEG C, in atmospheric conditions, it is passed through ammonia and hydrogen carries out ammonolysis reaction, wherein fed cyclohexanone liquid volume air speed is 0.3h-1,
The charging rate of ammonia be 50mL/min, ammonia ketone molar ratio be 13:1, hydrogen charge rate 10mL/min, to reaction product into
Row condensation carries out gas chromatographic analysis every 6 hours acquisition products, and obtaining yclohexanone conversion ratio is 100%, the selectivity of cyclohexylamine
It is 95%, after reaction 200 hours, catalyst activity does not decline.
Embodiment 2
In fixed bed device, 6 centimetres of above-mentioned gained A catalyst of height (1.2g) are packed into, are charging with hexandial, 170
DEG C, in atmospheric conditions, it is passed through ammonia and hydrogen carries out ammonolysis reaction, wherein hexandial feed liquid volume space velocity is 0.3h-1,
The charging rate of ammonia be 50mL/min, ammonium aldehyde molar ratio be 13:1, hydrogen charge rate 10mL/min, to reaction product into
Row condensation carries out gas chromatographic analysis every 6 hours acquisition products, and obtaining hexandial conversion ratio is 98%, the selectivity of hexamethylene diamine
It is 98%, after reaction 200 hours, catalyst activity does not decline.
Embodiment 3
In fixed bed device, 6 centimetres of above-mentioned gained A catalyst of height (1.2g) are packed into, are charging with benzaldehyde, 170
DEG C, in atmospheric conditions, it is passed through ammonia and hydrogen carries out ammonolysis reaction, wherein hexandial feed liquid volume space velocity is 0.3h-1,
The charging rate of ammonia be 50mL/min, ammonium aldehyde molar ratio be 13:1, hydrogen charge rate 10mL/min, to reaction product into
Row condensation carries out gas chromatographic analysis every 6 hours acquisition products, and obtaining benzaldehyde conversion ratio is 95%, the selectivity of benzene methanamine
It is 94%, after reaction 200 hours, catalyst activity does not decline.
Comparative example 1
In fixed bed device, 6 centimetres of above-mentioned gained B catalyst of height (1.2g) are packed into, remaining operation is obtained with embodiment 1
Yclohexanone conversion ratio is 95%, and the selectivity of cyclohexylamine is 85%, reacts 60 hours, conversion ratio 68% is selectively
60%, catalyst activity is decreased obviously.
Comparative example 2
In fixed bed device, 6 centimetres of above-mentioned gained C catalysts of height (1.2g) are packed into, remaining operation is obtained with embodiment 1
Yclohexanone conversion ratio is 100%, and the selectivity of cyclohexylamine is 92%, reacts 80 hours, conversion ratio 88% is selectively
95%.
Comparative example 3
In fixed bed device, 6 centimetres of above-mentioned gained D catalyst of height (1.2g) are packed into, remaining operation is urged with embodiment 1
Agent is almost without any activity.
Comparative example 4
In fixed bed device, 6 centimetres of above-mentioned gained E catalyst of height (1.2g) are packed into, remaining operation is urged with embodiment 1
Agent is almost without any activity.
Comparative example 5
In fixed bed device, 6 centimetres of above-mentioned gained F catalyst of height (1.2g) are packed into, remaining operation is obtained with embodiment 1
Yclohexanone conversion ratio is 89%, and the selectivity of cyclohexylamine is 90%, and after reacting 60 hours, conversion ratio 75% is selectively
93%, activity is decreased obviously.
Comparative example 6
In fixed bed device, 6 centimetres of above-mentioned gained G catalyst of height (1.2g) are packed into, remaining operation is obtained with embodiment 1
Yclohexanone conversion ratio is 93%, and the selectivity of cyclohexylamine is 85%, reacts 100 hours, conversion ratio 90% is selectively
83%, catalyst activity is declined.
Comparative example 7
In fixed bed device, 6 centimetres of above-mentioned gained H catalyst of height (1.2g) are packed into, remaining operation is obtained with embodiment 1
Yclohexanone conversion ratio is 60%, and the selectivity of cyclohexylamine is 88%, reacts 80 hours, conversion ratio 42% is selectively
75%, activity is declined.
Comparative example 8
In fixed bed device, 6 centimetres of above-mentioned gained I catalyst of height (1.2g) are packed into, remaining operation is obtained with embodiment 1
Yclohexanone conversion ratio is 72%, and the selectivity of cyclohexylamine is 86%, reacts 40 hours, conversion ratio 56% is selectively
80%, activity is declined.
Claims (10)
1. hydrotalcite composite catalyst is in the ammonolysis reaction between aldehydes or ketone compounds and ammonia in a hydrogen atmosphere
Purposes, it is characterised in that the hydrotalcite composite catalyst is by hydrotalcite or houghite composite transition metal simple substance activity
Component is formed by, and wherein transition metal simple substance active component includes main active component and helps active component, the main active group
It point is one of group viii b transition metal or a variety of in the periodic table of elements, described to help active component be to be selected from
One of I B~VIIB group 4 transition metal or a variety of in the periodic table of elements；
Preferably, the main active component accounts for 0.5~50wt% of composite catalyst gross mass, preferably 1-45wt%, more
It is preferred that 5~40wt%, more preferable 10~35wt%；Active component is helped to account for 0.01~30wt% of composite catalyst gross mass, it is excellent
It is selected as 0.1-25wt%, more preferable 1~20wt%, more preferable 3~15wt%.
2. purposes according to claim 1, it is characterised in that: the main active component is selected from ruthenium (Ru), rhodium (Rh), palladium
(Pd), one of platinum (Pt), nickel (Ni) or it is a variety of and it is described help active component be selected from copper (Cu), silver (Ag), gold (Au), zirconium
(Zr), one of tungsten (W) or a variety of.
3. purposes according to claim 1 or 2, it is characterised in that the purposes is hydrotalcite composite catalyst for ring
Hexanone and ammonia face the purposes that cyclohexylamine is prepared in hydrogen ammonolysis reaction or hydrotalcite composite catalyst for cyclohexanol and ring
The mixture of hexanone and the catalysis ammonolysis reaction of ammonia prepare the purposes of cyclohexylamine.
4. purposes described in any one of -3 according to claim 1, it is characterised in that the hydrotalcite composite catalyst is
It is prepared by a kind of preparation method included the following steps:
1) it is co-precipitated: by divalent metal salt, trivalent metal salt, main activity component metal salt and helping activity component metal salt and alkali
Property coprecipitator, which is dissolved in deionized water, is made into mixed liquor, will be formed by mixed liquor and is heated under stiring (such as in 35-150
8~15h is heated at DEG C) so that all metal ions are co-precipitated, while control pH value be lower than 7 (preferably 3.5-7, it is more excellent
Select 4-6, more preferable 4.5-5.5, such as 5 or so), slurries are obtained, then gained slurries (such as are cooled to 10~50 in cooling
DEG C, be preferably cooled to 20~40 DEG C of temperature) after thermostatic crystallization (such as 12~for 24 hours), later by the reaction solution after crystallization into
Row is filtered, washed and dried, and is then optionally ground, obtains hydrotalcite or houghite base complex；Wherein described two
Valence metal salt and the trivalent metal salt are to form hydrotalcite or the required divalent metal salt of houghite respectively
And trivalent metal salt, main activity component metal salt be in the periodic table of elements one of group viii b transition metal or
The salt of various metals, described to help activity component metal salt be selected from the periodic table of elements in I B~VIIB group 4 transition metal
The salt of one or more metals；
2) hydrotalcite of step 1) preparation or houghite base complex are roasted, obtains hydrotalcite or houghite base composite oxygen
Compound；With
3) hydrotalcite or houghite the base composite oxidate reduction obtained step 2), obtains hydrotalcite or houghite base is multiple
Close transition metal simple substance catalyst, that is, composite catalyst.
5. purposes according to claim 4, it is characterised in that: carrying out the temperature that the heating is co-precipitated in step 1) is
35-150 DEG C, preferably 50-120 DEG C, more preferable 80~110 DEG C；It is preferred that temperature dry described in step 1) is 100-130
DEG C, preferably 105-125 DEG C, more preferable 110~120 DEG C；And/or
In step 2): the temperature of roasting is 300-900 DEG C, preferably 400-800 DEG C, more preferably 500-700 DEG C；And/or roasting
The time of burning is 0.5-15h, preferably 1-10h, more preferably 1.5-8h.
6. purposes according to claim 4 or 5, it is characterised in that: the hydrotalcite or class for obtaining step 2) in step 3)
Hydrotalcite composite oxides are restored using hydrogen；It is preferred that the temperature of reduction reaction is 200-800 DEG C, preferably 300-
700 DEG C, more preferably 400-600 DEG C；It is preferred that the time of reduction reaction is 1-15h, preferably 2-10h, more preferably 3-8h；
And/or
In step 1), divalent metal salt, trivalent metal salt, activity component metal salt and the molar ratio of activity component metal salt is helped to be
2-4:0.5-2.0:0.1-2:0.05-1.3, preferably 2-4:0.7-1.5:0.2-1.6:0.08-1.0, such as 3:1:0.3:0.1；
And/or
In step 1), alkaline coprecipitator (for example, urea, sodium hydroxide and sodium carbonate, alternatively, ammonia or ammonium hydroxide and sodium carbonate)
Dosage be sufficient to make all metal ions in mixed liquor to be co-precipitated；Preferably, the dosage of alkaline coprecipitator is opposite
1.1-5 times in mixed liquor for the integral molar quantity of all metal ions, preferably 1.2-4 times, more preferable 1.3-3 times.
7. the method that aminated compounds is prepared by aldehydes or ketone compounds and the catalysis ammonolysis reaction of ammonia in a hydrogen atmosphere,
This method comprises: being reacted in a hydrogen atmosphere by aldehydes or ketone compounds with ammonia in the presence of hydrotalcite composite catalyst
Mixed in device and carry out ammonolysis reaction to be made aminated compounds,
It is characterized by: the hydrotalcite composite catalyst is by hydrotalcite or houghite composite transition metal simple substance active group
Divide and be formed by, wherein transition metal simple substance active component includes main active component and helps active component, the main active component
One of group viii b transition metal or a variety of in the periodic table of elements, it is described help active component be selected from member
One of I B~VIIB group 4 transition metal or a variety of in plain periodic table；
Preferably, the main active component accounts for 0.5~50wt% of composite catalyst gross mass, preferably 1-45wt%, more
It is preferred that 5~40wt%, more preferable 10~35wt%；Active component is helped to account for 0.01~30wt% of composite catalyst gross mass, it is excellent
It is selected as 0.1-25wt%, more preferable 1~20wt%, more preferable 3~15wt%.
8. according to the method described in claim 7, it is characterized by: the main active component is selected from ruthenium (Ru), rhodium (Rh), palladium
(Pd), one of platinum (Pt), nickel (Ni) or it is a variety of and it is described help active component be selected from copper (Cu), silver (Ag), gold (Au), zirconium
(Zr), one of tungsten (W) or a variety of.
9. method according to claim 7 or 8, it is characterised in that: the reactor is pressure autoclave type reactor, fluidized bed
Or one of fixed bed reactors；Preferred reactor is fixed bed reactors；And/or
Wherein the molar ratio of aldehydes or ketone compounds and ammonia be 0.01~5:1, preferably 0.03~4:1, more preferable 0.05~
3:1, more preferable 0.07~2.5:1.
10. method according to claim 7 or 8, it is characterised in that: reaction temperature is 50~400 DEG C, preferably 100 DEG C
~300 DEG C, more preferably 150 DEG C~200 DEG C；And/or
The pressure of reaction is normal pressure~5MPa, preferably normal pressure~4MPa, more preferably normal pressure~3MPa.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102822097A (en) * | 2010-03-09 | 2012-12-12 | 马克斯-普朗克科学促进学会 | Palladium-modified hydrotalcites and their use as catalyst precursors |
| CN106000406A (en) * | 2016-05-23 | 2016-10-12 | 北京化工大学 | Ni-based composite metal oxide catalyst and application thereof |
| CN106622228A (en) * | 2017-01-05 | 2017-05-10 | 湘潭大学 | Cycloalkane dehydrogenation catalyst, preparation method thereof and application |
| CN106669681A (en) * | 2016-12-14 | 2017-05-17 | 华南理工大学 | Ni/Cu/Al/Fe hydrotalcite precursor catalyst with magnetism and preparation method and application thereof |
| CN106867574A (en) * | 2015-12-14 | 2017-06-20 | 北京化工大学 | A kind of efficient catalytic sorbierite liquid phase is restructured as C6The method of hydrocarbon |
-
2018
- 2018-01-02 CN CN201810001682.6A patent/CN109985628A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102822097A (en) * | 2010-03-09 | 2012-12-12 | 马克斯-普朗克科学促进学会 | Palladium-modified hydrotalcites and their use as catalyst precursors |
| CN106867574A (en) * | 2015-12-14 | 2017-06-20 | 北京化工大学 | A kind of efficient catalytic sorbierite liquid phase is restructured as C6The method of hydrocarbon |
| CN106000406A (en) * | 2016-05-23 | 2016-10-12 | 北京化工大学 | Ni-based composite metal oxide catalyst and application thereof |
| CN106669681A (en) * | 2016-12-14 | 2017-05-17 | 华南理工大学 | Ni/Cu/Al/Fe hydrotalcite precursor catalyst with magnetism and preparation method and application thereof |
| CN106622228A (en) * | 2017-01-05 | 2017-05-10 | 湘潭大学 | Cycloalkane dehydrogenation catalyst, preparation method thereof and application |
Non-Patent Citations (1)
| Title |
|---|
| 陈娇领 等: "环戊酮催化氨解合成环戊胺", 《应用化工》 * |
Cited By (15)
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| CN110711588B (en) * | 2019-10-24 | 2021-02-12 | 中国科学院大连化学物理研究所 | Application of hydrotalcite-based catalyst in conversion of high-concentration sugar to 1, 2-propylene glycol |
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| CN111072487A (en) * | 2019-12-16 | 2020-04-28 | 中国科学院大连化学物理研究所 | Method for preparing hexamethylene diamine based on cyclohexene |
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