CN106866428A - A kind of method that carrier nanometer catalyst catalyzes and synthesizes tetramethyl dipropylenetriamine - Google Patents
A kind of method that carrier nanometer catalyst catalyzes and synthesizes tetramethyl dipropylenetriamine Download PDFInfo
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- CN106866428A CN106866428A CN201710140157.8A CN201710140157A CN106866428A CN 106866428 A CN106866428 A CN 106866428A CN 201710140157 A CN201710140157 A CN 201710140157A CN 106866428 A CN106866428 A CN 106866428A
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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
- C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
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- 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
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
It is by mol ratio 1 the invention discloses a kind of method that carrier nanometer catalyst catalyzes and synthesizes tetramethyl dipropylenetriamine:1 dimethylated propyl diethylenetriamine and dimethylaminopropionitrile is added in autoclave, is subsequently adding carrier nanometer catalyst, and air in kettle is replaced using High Purity Hydrogen after envelope kettle, then pass to hydrogen, reacting kettle inner pressure is set to control in 0.1 20MPa, the 24h of stirring reaction 1 at 80 400 DEG C obtains target product.The selectivity of synthetic method tetramethyl dipropylenetriamine of the present invention is up to more than 90%.
Description
First, technical field
The present invention relates to a kind of synthetic method of known compound, specifically a kind of carrier nanometer catalyst catalysis
The method for synthesizing tetramethyl dipropylenetriamine.
2nd, background technology
Surfactant is described as industrial monosodium glutamate, is widely applied in modern industry.No matter which kind of surface-active
Agent, its molecular structure is constituted by two parts, i.e., possess the hydrophilic of hydrophobic lipophilic group and polar hydrophilic in same molecule simultaneously
Base, thus impart such particular molecule not only hydrophilic but also oleophylic characteristic.By the species, the quantity that convert lipophilic group or hydrophilic group
And position in the molecular structure or the connected mode of the two, surfactant just has wetting or anti-glutinous, emulsification or demulsification, rises
Bubble or froth breaking and a series of physical such as solubilising, dispersion, washing, anti-corrosion, antistatic chemical property and corresponding practical application, into
It is class fine chemical product versatile and flexible, widely used.
Single hydrophobic chain surfactant with double-hydrophilic solubility property in hard water is good, and strong detergency is rinsability
Can be excellent, it is good to dirt particles dispersive property.Reparation, the change of crystallization behavior, chemical decontamination of recovery, environment in greasy dirt etc.
Critically important effect is played in application process.Betaine type amphoteric surfactant is a kind of double-hydrophilic surfactant, with compared with
Strong dirt-removing power and surfactant higher.Glycine betaine is widely used in washing and cosmetic field.The propylene three of tetramethyl two
Amine is the primary raw material of synthesizing betaine.Additionally, tetramethyl dipropylenetriamine is also widely used in other field, can be used for
In the soft bubble of molding and polyether-polyurethane magma bubble.Epoxy resin is can also be used for make to be catalyzed in curing agent and accelerator, Polyurethane
Decoppering agent of agent and semi-conducting material etc..But during its synthetic technology mainly rests in some foreign enterprise's hands, the country it is studied compared with
It is few.The current country is the byproduct for synthesizing diamines, and yield is few, and content is low.
3rd, the content of the invention
The present invention is intended to provide a kind of method that carrier nanometer catalyst catalyzes and synthesizes tetramethyl dipropylenetriamine, passes through
Carrier nanometer catalyst is catalyzed dimethylated propyl diethylenetriamine and dimethylaminopropionitrile synthesis tetramethyl dipropylenetriamine, realizes higher
The selectivity of reaction and the conversion ratio of product.Catalyst activity of the present invention is high, easily separated with product, have and preferably repeat profit
It is also relatively gentleer with property, simultaneous reactions condition, can effectively solve the problem that some defects of prior art.
The method that carrier nanometer catalyst of the present invention catalyzes and synthesizes tetramethyl dipropylenetriamine, comprises the following steps：
By mol ratio 1:1 dimethylated propyl diethylenetriamine and dimethylaminopropionitrile is added in autoclave, is subsequently adding load
Type nanocatalyst, air in kettle is replaced after envelope kettle using High Purity Hydrogen, then passes to hydrogen, controls reacting kettle inner pressure
Stirring reaction 1-24h at 0.1-20MPa, 80-400 DEG C, by gas chromatographic detection assay products after the completion of reaction.
Preferably, reaction temperature is 110-200 DEG C, the reaction time is 10-16h.
Preferably, reacting kettle inner pressure is set to 1-4MPa.
Preferably, in course of reaction, mixing speed is set to 200-500rmp/min.
The addition of carrier nanometer catalyst is the 1-10% of dimethylated propyl diethylenetriamine and dimethylaminopropionitrile gross mass, excellent
Select 5%.
The carrier nanometer catalyst that the present invention is used, is catalyzed obtained from active component is loaded on nano-carrier
The quality of agent, wherein active component accounts for the 0.1-50% of nano-carrier quality, preferably 10%.
The active component is that noble metal and/or base metal are constituted, and wherein noble metal is Pt, Pd or Ru, base metal
It is Cu, Ni, Fe or Co.
The active component is preferably noble metal and base metal and constitutes, and noble metal and non-noble metal is rubbed in active component
Your ratio is 1:0.2-20, preferably 1:2.
The nano-carrier is selected from SiO2、TiO2、γ-Al2O3Or carbon based material (such as activated carbon, graphite, mesoporous carbon, nanometer
Carbon pipe, Graphene etc.), preferably SiO2。
The carrier nanometer catalyst that the present invention is used, can be abbreviated as M@P, and wherein M represents active component, and P is represented and received
Meter Zai Ti.
The preparation method of the carrier nanometer catalyst that the present invention is used, comprises the following steps：
(1) by active component donor addition aqueous solvent, it is configured to the presoma that concentration is 0.001~0.1mol/L molten
Liquid, dispersed with stirring is uniform；The active component donor is the inorganic salts or organic salt of the active component, such as PdCl2、Pd
(NO3)2、Pd(OAc)2、RuCl3、Ni(NO3)2、NiCl2、Cu(NO3)2、CuCl2And C4H6O4The salt compounds such as Co.
(2) to nano-carrier is added in the precursor solution of step (1) preparation, it is placed in after stirring in baking oven at 50 DEG C
Drying and dehydrating 12h, then the calcining reduction in tube furnace, obtains carrier nanometer catalyst.During calcining reduction using hydrogen and
Nitrogen mixed gas are reduced, and hydrogen is 1 with nitrogen flow ratio：0.5-10, preferably 1:2.Calcining reduction temperature is 250-600 DEG C,
It is preferred that 350-550 DEG C.The calcining reduction time is 1-12h, preferably 4-5h.
Beneficial effects of the present invention are embodied in：
The present invention can effectively improve tetramethyl dipropylenetriamine due to the addition of noble metal active component in catalyst
Reactivity；The addition of base metal active component can promote the dispersion of active component, and non-noble metal components are to the raw material
Middle N-H keys have activity very high, improve the conversion ratio of raw material.The present invention has catalytic reaction activity higher, selective higher
The advantages of easily separated with catalyst and product, industrialized production is advantageously implemented, reduces production cost.
4th, specific embodiment
By following examples, the invention will be further described；
Embodiment 1：Ni@SiO2The preparation of metal nano catalyst
1st, the raw material of metal nano catalyst is configured in the present embodiment：
Ni(NO3)2·6H2O 0.5mmol(0.146g)
SiO2 2g
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density Ni (NO are configured according to the above-mentioned active component donor amount for weighing3)2·6H2O solution, then to it
In be slowly added dropwise 5% dust technology to PH be 5-6, stir 2h, obtain mixed material；To addition 2g carriers in the mixed material
SiO2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace, activation method is
(volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, load type metal nano-catalytic is obtained final product
Agent.Embodiment 2：Pd-Ni@SiO2(mol ratio of Pd and Ni is 1 for the preparation of bimetal nano catalyst:1)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
PdCl2 0.5mmol(0.088g)
Ni(NO3)2·6H2O 0.5mmol(0.146g)
SiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density Ni (NO are configured according to the above-mentioned active component donor amount for weighing3)2·6H2O and PdCl2Mixing is molten
Liquid, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To in the mixed material
Add 2g carrier Ss iO2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace,
Activation method is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, the double gold of support type are obtained final product
Category nanocatalyst.
Embodiment 3：Pd-Ni@SiO2(mol ratio of Pd and Ni is 1 for the preparation of bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
PdCl2 0.5mmol(0.088g)
Ni(NO3)2·6H2O 1.0mmol(0.291g)
SiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density Ni (NO are configured according to the above-mentioned active component donor amount for weighing3)2·6H2O and PdCl2Mixing is molten
Liquid, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To in the mixed material
Add 2g carrier Ss iO2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace,
Activation method is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, the double gold of support type are obtained final product
Category nanocatalyst.
Embodiment 4：Pd-Ni@SiO2(mol ratio of Pd and Ni is 1 for the preparation of bimetal nano catalyst:4)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
PdCl2 0.5mmol(0.088g)
Ni(NO3)2·6H2O 2.0mmol(0.582g)
SiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density Ni (NO are configured according to the above-mentioned active component donor amount for weighing3)2·6H2O and PdCl2Mixing is molten
Liquid, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To in the mixed material
Add 2g carrier Ss iO2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace,
Activation method is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, load type metal is obtained final product
Nanocatalyst.
Embodiment 5：Pd-Ni@SiO2(mol ratio of Pd and Ni is 1 for the preparation of bimetal nano catalyst:0)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
PdCl2 0.5mmol(0.088g)
SiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density PdCl is configured according to the above-mentioned active component donor amount for weighing2Mixed solution, then delays thereto
5% dust technology of slow dropwise addition is 5-6 to PH, stirs 2h, obtains mixed material；To addition 2g carrier Ss iO in the mixed material2,
Continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace, activation method is hydrogen nitrogen
(volume ratio of hydrogen and nitrogen is 1 to mixed atmosphere:2) 4h is reduced in 450 DEG C under, load type metal nanocatalyst is obtained final product.
Embodiment 6：Dimethylated propyl diethylenetriamine and dimethylaminopropionitrile catalyze and synthesize tetramethyl dipropylenetriamine
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, the metal nano for adding 1g embodiments 1 to prepare
Catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through pressure in hydrogen to kettle after air
3.5MPa, is heated to 120 DEG C under the conditions of stirring (400rmp/min), react 12h.Analyzed by gas chromatographic detection after the completion of reaction
Product.
Above-mentioned experimental procedure is repeated, (mol ratio of Pd and Ni is 0 by the made catalyst of embodiment 1-5:1、1:1、1:2、1:
4、1:0) test successively, obtained experimental data is as shown in table 1；
The different catalysts catalytic reaction of table 1
As it can be seen from table 1 Pd can promote the synthesis of tetramethyl dipropylenetriamine, but the presence tetramethyl two of only Pd
The yield and selectivity of propylene triamine are all relatively low, and the yield and selectivity of tetramethyl dipropylenetriamine are substantially carried after introducing Ni
It is high；In addition, when the mol ratio of Pd and Ni is 1:When 2, catalytic effect is best.
Embodiment 7：Pt-Cu@TiO2(mol ratio of Pt and Cu is 1 for the preparation of bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
H2PtCl6·6H2O 1.0mmol(0.518g)
CuCl2 2.0mmol(0.340g)
TiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density H is configured according to the above-mentioned active component donor amount for weighing2PtCl6·6H2O and CuCl2Mixing is molten
Liquid, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To in the mixed material
Add 2g carriers TiO2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace,
Activation method is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, the double gold of support type are obtained final product
Category nanocatalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 2.5MPa, is heated to 140 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 34%, selectivity is 67%.
Embodiment 8：Pt-Ni@TiO2(mol ratio of Pt and Ni is 1 for the preparation of bimetal nano catalyst:1)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
H2PtCl6·6H2O 1.0mmol(0.518g)
Ni(NO3)2·6H2O 0.5mmol(0.146g)
TiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density H is configured according to the above-mentioned active component donor amount for weighing2PtCl6·6H2O and Ni (NO3)2·6H2O
Mixed solution, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To the mixing
2g carriers TiO is added in material2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then by tubular type
Stove is activated, and activation method is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, is obtained final product negative
Load type bimetal nano catalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 2.5MPa, is heated to 140 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 37%, selectivity is 66%.
Embodiment 9：Pt-Ni@TiO2(mol ratio of Pt and Ni is 1 for the preparation of bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
H2PtCl6·6H2O 1.0mmol(0.518g)
Ni(NO3)2·6H2O 1.0mmol(0.291g)
TiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density H is configured according to the above-mentioned active component donor amount for weighing2PtCl6·6H2O and Ni (NO3)2·6H2O
Mixed solution, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To the mixing
2g carriers TiO is added in material2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then by tubular type
Stove is activated, and activation method is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, is obtained final product negative
Load type bimetal nano catalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 2.5MPa, is heated to 140 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 40%, selectivity is 72%.
Embodiment 10：Pt-Co@γ-Al2O3(mol ratio of Pt and Co is 1 for the preparation of bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
H2PtCl6·6H2O 1.0mmol(0.518g)
C4H6O4Co 2.0mmol(0.354g)
γ-Al2O3 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density H is configured according to the above-mentioned active component donor amount for weighing2PtCl6·6H2O and C4H6O4Co mixing is molten
Liquid, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To in the mixed material
Add 2g carrier γ-Al2O3, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then lived by tube furnace
Change, activation method is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, support type is obtained final product
Bimetal nano catalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 3.5MPa, is heated to 170 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 46%, selectivity is 65%.
Embodiment 11：(mol ratio of Pt and Co is 1 for the preparation of Pt-Co@C bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
H2PtCl6·6H2O 1.0mmol(0.518g)
C4H6O4Co 2.0mmol(0.354g)
Activated carbon 2g.
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density H is configured according to the above-mentioned active component donor amount for weighing2PtCl6·6H2O and C4H6O4Co mixing is molten
Liquid, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To in the mixed material
2g support Cs are added, continues to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace, it is living
Change mode is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, load type double-metal is obtained final product
Nanocatalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 3.5MPa, is heated to 170 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 39%, selectivity is 58%.
Embodiment 12：Pt-Co@TiO2(mol ratio of Pt and Co is 1 for the preparation of bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
H2PtCl6·6H2O 1.0mmol(0.518g)
C4H6O4Co 2.0mmol(0.354g)
TiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density H is configured according to the above-mentioned active component donor amount for weighing2PtCl6·6H2O and C4H6O4Co mixing is molten
Liquid, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To in the mixed material
Add 2g carriers TiO2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace,
Activation method is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, the double gold of support type are obtained final product
Category nanocatalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 3.5MPa, is heated to 170 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 43%, selectivity is 64%.
Embodiment 13：Pt-Co@SiO2(mol ratio of Pt and Co is 1 for the preparation of bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
H2PtCl6·6H2O 1.0mmol(0.518g)
C4H6O4Co 2.0mmol(0.354g)
SiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density H is configured according to the above-mentioned active component donor amount for weighing2PtCl6·6H2O and C4H6O4Co mixing is molten
Liquid, it is 5-6 that 5% dust technology is then slowly added dropwise thereto to PH, stirs 2h, obtains mixed material；To in the mixed material
Add 2g carrier Ss iO2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace,
Activation method is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, the double gold of support type are obtained final product
Category nanocatalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 3.5MPa, is heated to 170 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 47%, selectivity is 71%.
Embodiment 14：(mol ratio of Ru and Cu is 1 for the preparation of Ru-Cu@C bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
RuCl3·3H2O 1.0mmol(0.207g)
CuCl2 2.0mmol(0.340g)
Activated carbon 2g.
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density RuCl is configured according to the above-mentioned active component donor amount for weighing3·3H2O and CuCl2Mixed solution,
Then it is 5-6 to be slowly added dropwise 5% dust technology thereto to PH, stirs 2h, obtains mixed material；Added in the mixed material
2g carrier active carbons, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace, it is living
Change mode is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, load type double-metal is obtained final product
Nanocatalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 3.5MPa, is heated to 160 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 24%, selectivity is 68%.
Embodiment 15：Ru-Cu@TiO2(mol ratio of Ru and Cu is 1 for the preparation of bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
RuCl3·3H2O 1.0mmol(0.207g)
CuCl2 2.0mmol(0.340g)
TiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density RuCl is configured according to the above-mentioned active component donor amount for weighing3·3H2O and CuCl2Mixed solution,
Then it is 5-6 to be slowly added dropwise 5% dust technology thereto to PH, stirs 2h, obtains mixed material；Added in the mixed material
2g carriers TiO2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace, activation
Mode is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, load type double-metal is obtained final product and is received
Rice catalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 3.5MPa, is heated to 160 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 21%, selectivity is 60%.
Embodiment 16：Ru-Cu@SiO2(mol ratio of Ru and Cu is 1 for the preparation of bimetal nano catalyst:2)
1st, the raw material of bimetal nano catalyst is configured in the present embodiment：
RuCl3·3H2O 1.0mmol(0.207g)
CuCl2 2.0mmol(0.340g)
SiO2 2g。
2nd, the preparation method of bimetal nano catalyst is as follows in the present embodiment：
Certain density RuCl is configured according to the above-mentioned active component donor amount for weighing3·3H2O and CuCl2Mixed solution,
Then it is 5-6 to be slowly added dropwise 5% dust technology thereto to PH, stirs 2h, obtains mixed material；Added in the mixed material
2g carrier Ss iO2, continue to stir 5h.Above-mentioned catalyst precarsor is placed in 55 DEG C and dries 12h, then activated by tube furnace, activation
Mode is that (volume ratio of hydrogen and nitrogen is 1 to hydrogen nitrogen mixed gas atmosphere:2) 4h is reduced in 450 DEG C under, load type double-metal is obtained final product and is received
Rice catalyst.
3rd, tetramethyl dipropylenetriamine is catalyzed and synthesized
30ml dimethylated propyl diethylenetriamines and 28ml dimethylaminopropionitriles are mixed, adds 1g bimetallics manufactured in the present embodiment to receive
Rice catalyst is put into 100ml autoclaves, is replaced in kettle using High Purity Hydrogen after envelope kettle and is passed through hydrogen to kettle internal pressure after air
Power 3.5MPa, is heated to 160 DEG C under the conditions of stirring (400rmp/min), react 12h.By gas chromatographic detection point after the completion of reaction
Division thing.Understand that products collection efficiency is 30%, selectivity is 70%.
Claims (10)
1. a kind of method that carrier nanometer catalyst catalyzes and synthesizes tetramethyl dipropylenetriamine, it is characterised in that including following step
Suddenly：
By mol ratio 1:1 dimethylated propyl diethylenetriamine and dimethylaminopropionitrile is added in autoclave, is subsequently adding support type and is received
Rice catalyst, air in kettle is replaced after envelope kettle using High Purity Hydrogen, then passes to hydrogen, reacting kettle inner pressure is controlled in 0.1-
Stirring reaction 1-24h at 20MPa, 80-400 DEG C, obtains target product.
2. method according to claim 1, it is characterised in that：
The addition of carrier nanometer catalyst is the 1-10% of dimethylated propyl diethylenetriamine and dimethylaminopropionitrile gross mass.
3. method according to claim 2, it is characterised in that：
The addition of carrier nanometer catalyst is the 5% of dimethylated propyl diethylenetriamine and dimethylaminopropionitrile gross mass.
4. method according to claim 1, it is characterised in that：
The carrier nanometer catalyst is catalyst obtained from active component is loaded on nano-carrier, wherein activearm
The quality divided accounts for the 0.1-50% of nano-carrier quality.
5. method according to claim 4, it is characterised in that：
The quality of active component accounts for the 10% of nano-carrier quality.
6. method according to claim 4, it is characterised in that：
The active component is that noble metal and/or base metal are constituted, and wherein noble metal is Pt, Pd or Ru, base metal be Cu,
Ni, Fe or Co.
7. the method according to claim 4 or 6, it is characterised in that：
The active component is that noble metal and base metal are constituted, and noble metal and non-noble metal mol ratio are 1 in active component:
0.2-20。
8. method according to claim 4, it is characterised in that：
The nano-carrier is selected from SiO2、TiO2、γ-Al2O3Or carbon based material.
9. method according to claim 1, it is characterised in that：
Reaction temperature is 110-200 DEG C, and the reaction time is 10-16h.
10. method according to claim 1, it is characterised in that：
Reacting kettle inner pressure is set to 1-4MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285772A (en) * | 2019-12-19 | 2020-06-16 | 嘉兴润博化工科技有限公司 | Synthesis method of tetramethyldiene triamine compound |
| CN115028537A (en) * | 2022-05-26 | 2022-09-09 | 万华化学集团股份有限公司 | Preparation method of aminopropyl alicyclic secondary amine |
| CN115869960A (en) * | 2022-12-16 | 2023-03-31 | 南京红宝丽醇胺化学有限公司 | Ni-Co-Ce-Cr catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040220428A1 (en) * | 2002-12-20 | 2004-11-04 | Till Gerlach | Preparation of a symmetrical secondary amine |
| WO2005061430A1 (en) * | 2003-12-19 | 2005-07-07 | Basf Aktiengesellschaft | Method for increasing the space-time yield in a process used for the production of a symmetric secondary amine |
| CN101111469A (en) * | 2005-02-01 | 2008-01-23 | 巴斯福股份公司 | Method for producing bis-[(3-dimethylamino)propyl]amine (bisdmapa) |
| CN102029160A (en) * | 2010-11-17 | 2011-04-27 | 南京大学 | Catalyst for use in preparation of paraphenyldimethylamine and preparation method thereof |
-
2017
- 2017-03-10 CN CN201710140157.8A patent/CN106866428A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040220428A1 (en) * | 2002-12-20 | 2004-11-04 | Till Gerlach | Preparation of a symmetrical secondary amine |
| WO2005061430A1 (en) * | 2003-12-19 | 2005-07-07 | Basf Aktiengesellschaft | Method for increasing the space-time yield in a process used for the production of a symmetric secondary amine |
| CN101111469A (en) * | 2005-02-01 | 2008-01-23 | 巴斯福股份公司 | Method for producing bis-[(3-dimethylamino)propyl]amine (bisdmapa) |
| CN102029160A (en) * | 2010-11-17 | 2011-04-27 | 南京大学 | Catalyst for use in preparation of paraphenyldimethylamine and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| TAKASHI IKAWA等: "Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines", 《ORG.BIOMOL.CHEM.》 * |
| 冯乙巳，张立德: "介孔二氧化硅干凝胶和气凝胶纳米复合材料的研究进展", 《功能材料》 * |
| 刘威威: "Pd-Ni/γ-Al2O3催化四甲基二丙烯三胺的合成研究", 《中国优秀硕学位论文全文数据库 工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285772A (en) * | 2019-12-19 | 2020-06-16 | 嘉兴润博化工科技有限公司 | Synthesis method of tetramethyldiene triamine compound |
| CN111285772B (en) * | 2019-12-19 | 2023-03-14 | 山东中科新材料研究院有限公司 | Synthesis method of tetramethyldiene triamine compound |
| CN115028537A (en) * | 2022-05-26 | 2022-09-09 | 万华化学集团股份有限公司 | Preparation method of aminopropyl alicyclic secondary amine |
| CN115028537B (en) * | 2022-05-26 | 2023-08-11 | 万华化学集团股份有限公司 | Preparation method of aminopropyl alicyclic secondary amine |
| CN115869960A (en) * | 2022-12-16 | 2023-03-31 | 南京红宝丽醇胺化学有限公司 | Ni-Co-Ce-Cr catalyst and preparation method and application thereof |
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