CN115869960A - Ni-Co-Ce-Cr catalyst and preparation method and application thereof - Google Patents
Ni-Co-Ce-Cr catalyst and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
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- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 19
- 229940043276 diisopropanolamine Drugs 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
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- 239000002243 precursor Substances 0.000 claims description 9
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- 238000001035 drying Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 3
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- 150000003839 salts Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
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- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- AMLFJZRZIOZGPW-NSCUHMNNSA-N (e)-prop-1-en-1-amine Chemical compound C\C=C\N AMLFJZRZIOZGPW-NSCUHMNNSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
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- 239000011148 porous material Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
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- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- 229910018054 Ni-Cu Inorganic materials 0.000 description 2
- 229910018481 Ni—Cu Inorganic materials 0.000 description 2
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical group [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229940102253 isopropanolamine Drugs 0.000 description 2
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 208000012839 conversion disease Diseases 0.000 description 1
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- 239000012971 dimethylpiperazine Substances 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a Ni-Co-Ce-Cr catalyst and a preparation method and application thereof, belonging to the technical field of catalysis. The catalyst prepared by the invention contains 60-65% of Ni, 25-30% of Co, 5-9% of Ce and 1-5% of Cr. The Ni-Co-Ce-Cr catalyst disclosed by the invention is high in catalytic activity, and the obtained catalyst is used for synthesizing diaminodipropylamine, so that the catalyst has excellent activity and selectivity. The synthesis process of the diamino dipropylamine disclosed by the invention has the advantages of high selectivity, high activity, few byproducts, simple synthesis process and low process cost.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a Ni-Co-Ce-Cr catalyst and a preparation method and application thereof.
Background
Diaminodipropylamine is also known as dipropylenetriamine, is used as an epoxy curing agent, an emulsifier, an insecticide and the like, can be used for synthesizing a biological adsorption separation material and various surfactants, is also an intermediate for manufacturing dyes and rubber, and is an important chemical intermediate. The early curing agents and the like are frequently used and are now replaced by dipropylene triamine.
Chinese patent CN110327931B provides a catalyst, a preparation method thereof and a production process of propyleneamine using the catalyst. This patent uses isopropanolamine as raw material to synthesize series of propyleneamine products, such as 1, 2-propylenediamine, dimethylpiperazine, diaminodipropylamine, polypropylenepolylamine, etc. The catalyst is Co-Ni-Cu/Al 2 O 3 The contents of Co, ni, cu and Al are 0-30.0%, 0-25.0%, 0-5.0% and the rest 2 O 3 . The synthesized product is mainly 1, 2-propane diamine (the content is more than 90 percent), and the diamino dipropylamine accounts for less (the content is more than 2 percent). The catalyst and the synthesis process are suitable for the synthesis production of 1, 2-propane diamine, and the selectivity of the diamino dipropylamine is extremely poor, so that the catalyst and the synthesis process are not suitable for the industrial production of the diamino dipropylamine.
Disclosure of Invention
The invention aims to: the invention aims to provide a Ni-Co-Ce-Cr catalyst and a preparation method and application thereof aiming at the defects of the prior art. The Ni-Co-Ce-Cr catalyst prepared by the invention has high catalytic activity, and the obtained catalyst is used for synthesizing diaminodipropylamine, so that the catalyst has excellent activity and selectivity.
The technical scheme is as follows: the purpose of the invention is realized by the following technical scheme:
the invention provides a Ni-Co-Ce-Cr catalyst, wherein the catalyst contains 60-65% of Ni, 25-30% of Co, 5-9% of Ce and 1-5% of Cr.
Experiments show that under the limitation of the content ratio of the components, the catalytic function of the catalyst can be maximized, especially the addition of Ce can effectively improve the activity of the catalyst and improve the reaction conversion rate and the product selectivity.
The invention also provides a preparation method of the Ni-Co-Ce-Cr catalyst, which comprises the following steps:
(1) Adding an alkaline precipitator into a metal salt solution containing Ni, co, ce and Cr in proportion to completely precipitate metal ions, and aging;
(2) After aging, filtering to obtain a precipitate, washing and drying the precipitate to obtain a precursor;
(3) And roasting, grinding and activating the precursor to obtain the catalyst.
One specific implementation way of the step (1) of the invention is that metal salts of Ni, co, ce and Cr are added into water according to a proportion and dissolved at the temperature of 60-80 ℃ to prepare a metal salt solution; then, the temperature of the metal salt solution is maintained, an alkaline precipitant solution with the mass concentration of 40% is dripped into the metal salt solution, and aging is performed after the dripping is completed.
Preferably, in the step (1), the metal salt is nitrate or acetate, and the concentration of the metal salt solution is 30-50%; the alkaline precipitator is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate or ammonium bicarbonate.
Preferably, the mass fraction of the alkaline precipitant is 40-60%.
On the basis of a nickel-based catalyst, a certain amount of Co, ce and Cr is added to be matched with Ni, so that the overall activity of the catalyst is improved. In experiments, the coprecipitation method is adopted, so that the catalytic effect of the nickel-based catalyst can be greatly improved, and after Co, ce and Cr are added, the catalytic effect of the catalyst can be further improved, and the activity and the selectivity of the catalyst are enhanced.
Preferably, in the step (1), the temperature of the precipitation is 60-80 ℃, the temperature of the aging is 60-80 ℃, and the aging time is 1-4 h.
In the present invention, it is preferable that the precipitation temperature is the same as the aging temperature, that is, the aging and precipitation are completed at the same temperature. The purpose of aging is to allow the precipitate particles to grow and to perfect or transform the crystal form. In the present invention, there is no particular requirement for the aging process of the precipitate, and the aging process can be completed by the conventional techniques without limitation.
Under the conditions, the crystal nucleus generation speed and the growth speed can be effectively controlled, so that a proper crystal structure is obtained. Provides a good foundation for subsequent roasting, and ensures that the roasted material has a large number of fine pore passages so as to ensure the specific surface area of the catalyst and improve the service efficiency of the catalyst.
Preferably, in the step (2), the drying temperature is 80-120 ℃, and the drying time is 6-14 h. The method of filtration, washing and drying is not particularly limited, and a method known in the art may be used.
Preferably, in the step (3), the roasting temperature is 400-500 ℃, and the roasting time is 4-8 h; the activation is carried out in the atmosphere of hydrogen, the activation temperature is 500-600 ℃, and the activation time is 3-5 h.
Under the condition, the components in the precursor can be ensured to be reacted and converted, impurities are removed, the specific surface area is increased, the mechanical strength is improved, and the catalyst has higher activity. The roasting temperature is too high, so that the specific surface area of the catalyst is reduced, and the pore structure is damaged; the calcination temperature is too low to completely decompose the metal hydroxide. In the roasting temperature and the roasting time, all components in the precursor can be completely oxidized, impurities such as chemically combined water and the like are removed, the specific surface area is increased, and the mechanical strength is improved.
The activation temperature is too high, so that the specific surface area of the catalyst is reduced, and the pore structure is damaged; the activation temperature is too low or the activation time is too short to reduce the metal oxide. In the activation temperature and the activation time, the nickel oxide can be completely reduced into metallic nickel, and the structure of the catalyst is not influenced.
The invention also provides an application of the Ni-Co-Ce-Cr catalyst in the synthesis of diaminodipropylamine.
The Ni-Co-Ce-Cr catalyst prepared by the invention is used for synthesizing diaminodipropylamine. The synthesis of the diaminodipropylamine comprises the following steps:
(1) Adding a Ni-Co-Ce-Cr catalyst and diisopropanolamine, introducing liquid ammonia and hydrogen, heating and reacting;
(2) And after the reaction is finished, cooling, filtering, recovering the catalyst, and rectifying the filtrate under reduced pressure to obtain the diaminodipropylamine.
One specific embodiment of the synthesis of diaminodipropylamine according to the present invention is: the Ni-Co-Ce-Cr catalyst and diisopropanolamine are added into an autoclave and replaced by hydrogen. Liquid ammonia is firstly introduced, and then hydrogen is introduced. After the temperature is raised, the reaction is kept at the temperature. After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia from the filtered synthetic product by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa), and then heating to 130-140 ℃ for reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain the diaminodipropylamine.
Preferably, in order to ensure that the reaction is smoothly carried out, in the step (1), the adding amount of the catalyst is 6-8% of the mass of the diisopropanolamine, the molar ratio of the liquid ammonia to the diisopropanolamine is (4-8): 1,H 2 The initial pressure was 1MPa.
The dosage of the catalyst is controlled in the proportion, so that the smooth proceeding of the reaction can be ensured, and the selectivity of the reaction can be ensured. When the catalyst is used in a small amount, the catalytic effect is poor, and the conversion rate of diisopropanolamine is low; if the amount of the catalyst used is too large, the cost increases and the difficulty of recovering and treating the catalyst increases.
Preferably, in the step (1), the reaction temperature is 200-220 ℃, and the reaction time is 4-6 h.
If the temperature is too low or the time is too short, the reaction is incomplete, and the conversion rate of the raw materials is low; too high a temperature leads to increased side reactions. The reaction time is too long, which has little influence on the conversion rate and the yield, but can increase the working hours and the energy consumption.
Has the beneficial effects that:
the Ni-Co-Ce-Cr catalyst prepared by the invention has high catalytic activity, and the obtained catalyst is used for synthesizing diaminodipropylamine, so that the catalyst has excellent activity and selectivity. The invention adopts diisopropanolamine as a raw material to synthesize the diamino dipropylamine, thereby shortening the reaction flow and reducing the generation of byproducts. Therefore, the catalyst and the synthesis process of the diamino dipropylamine have the advantages of high selectivity, high activity, few byproducts, simple synthesis process, low process cost, greenness and economy.
Drawings
FIG. 1 is a gas spectrum of a diaminodipropylamine standard;
FIG. 2 is a gas spectrum of diaminodipropylamine synthesized in example 4.
Detailed Description
The technical solution of the present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to the examples.
EXAMPLE 1 preparation of Ni-Co-Ce-Cr catalyst
(1) Adding nickel acetate, cobalt nitrate, cerium nitrate and chromium nitrate into water according to the proportion of 60% of Ni content, 30% of Co content, 9% of Ce content and 1% of Cr content, heating to 60 ℃, stirring and dissolving to prepare a metal salt solution with the mass fraction of 30%. At 60 ℃, a sodium hydroxide solution with the mass fraction of 60% is added to completely precipitate metal ions, and the mixture is aged for 4 hours at the temperature.
(2) After aging, the precipitate was filtered, washed several times with water and ethanol, and dried at 80 ℃ for 14 hours to obtain a catalyst precursor.
(3) And roasting the dried precursor at 400 ℃ for 8h, grinding the roasted metal oxide to 80 meshes and screening. And then activating for 5 hours at 500 ℃ in the atmosphere of hydrogen to obtain the catalyst A1.
EXAMPLE 2 preparation of Ni-Co-Ce-Cr catalyst
(1) Adding nickel acetate, cobalt nitrate, cerium nitrate and chromium nitrate into water according to the proportion of 62% of Ni content, 28% of Co content, 7% of Ce content and 3% of Cr content, heating to 70 ℃, stirring and dissolving to prepare a metal salt solution with the mass fraction of 40%. At 70 ℃, a potassium hydroxide solution with the mass fraction of 50% is added to completely precipitate metal ions, and the mixture is aged for 2h at the temperature.
(2) After aging, the precipitate was filtered, washed several times with water and ethanol, and dried at 100 ℃ for 10 hours to obtain a catalyst precursor.
(3) And roasting the dried precursor at 450 ℃ for 6 hours, grinding the roasted metal oxide to 80 meshes and screening. And activating for 4 hours at 550 ℃ in the hydrogen atmosphere to obtain the catalyst A2.
EXAMPLE 3 preparation of Ni-Co-Ce-Cr catalyst
(1) Adding nickel acetate, cobalt nitrate, cerium nitrate and chromium nitrate into water according to the proportion of 65% of Ni content, 25% of Co content, 5% of Ce content and 5% of Cr content, heating to 80 ℃, stirring and dissolving to prepare a metal salt solution with the mass fraction of 50%. At 80 ℃, a sodium carbonate solution with the mass fraction of 40% is added to completely precipitate metal ions, and the mixture is aged for 1 hour at the temperature.
(2) After aging, the precipitate was filtered, washed several times with water and ethanol, and dried at 120 ℃ for 6 hours to obtain a catalyst precursor.
(3) And roasting the dried precursor at 500 ℃ for 4 hours, grinding the roasted metal oxide to 80 meshes and screening. And then activating for 3 hours at 600 ℃ in the atmosphere of hydrogen to obtain the catalyst A3.
The catalyst is prepared by a coprecipitation method, and the metal elements and the proportion are fixed, so that the problem of non-adsorption is solved. The performance of the catalyst is verified by adopting a synthesis experiment of diaminodipropylamine, and the composition of the catalyst is adjusted and optimized according to the experimental result.
Example 4 Synthesis of Diaminodipropylamine
(1) 133.2g of diisopropanolamine and 8.0g of catalyst A1 were charged into the autoclave and replaced with hydrogen 3 times. 68.0g of liquid ammonia are initially introduced and then hydrogen (initial pressure 1 MPa) is introduced. Heating to 220 ℃ and then carrying out heat preservation reaction for 6h.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa) of the filtered synthetic product, heating to 130-140 ℃, and performing reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain diaminodipropylamine on the top of the tower.
FIG. 1 is a gas spectrum of a diaminodipropylamine standard;
FIG. 2 is a gas spectrum of diaminodipropylamine synthesized in example 4;
diamino dipropylamine standard: allantin reagent cat No. D155042
A gas spectrometer: agilent 7820A gas chromatograph
The comparison with a standard substance spectrogram proves that the synthesis method effectively synthesizes the diamino dipropylamine.
EXAMPLE 5 Synthesis of Diaminodipropylamine
(1) 133.2g of diisopropanolamine and 9.3g of catalyst A1 were charged into the autoclave and replaced 3 times with hydrogen. 102.0g of liquid ammonia was introduced first, and then hydrogen (initial pressure 1 MPa) was introduced. Heating to 210 ℃ and then preserving the temperature for 5 hours.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia from the filtered synthetic product by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa), heating to 130-140 ℃, and performing reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain diaminodipropylamine on the tower top.
EXAMPLE 6 Synthesis of Diaminodipropylamine
(1) 133.2g of diisopropanolamine and 10.7g of catalyst A1 were charged into the autoclave and replaced 3 times with hydrogen. 136.0g of liquid ammonia were introduced first, and then hydrogen (initial pressure 1 MPa) was introduced. Heating to 200 ℃ and then preserving the temperature for reaction for 4h.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa) of the filtered synthetic product, heating to 130-140 ℃, and performing reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain diaminodipropylamine on the top of the tower.
Example 7
(1) 133.2g of diisopropanolamine and 8.0g of catalyst A2 were charged in the autoclave and replaced 3 times with hydrogen. 68.0g of liquid ammonia are initially introduced and then hydrogen (initial pressure 1 MPa) is introduced. Heating to 220 ℃ and then carrying out heat preservation reaction for 6h.
(2) And after the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa) of the filtered synthetic product, heating to 130-140 ℃, and performing reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain diaminodipropylamine on the top of the tower.
Example 8
(1) 133.2g of diisopropanolamine and 9.3g of catalyst A2 were charged into the autoclave and replaced 3 times with hydrogen. 102.0g of liquid ammonia was introduced first, and then hydrogen (initial pressure 1 MPa) was introduced. The temperature is raised to 210 ℃ and then the reaction is carried out for 5 hours.
(2) And after the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa) of the filtered synthetic product, heating to 130-140 ℃, and performing reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain diaminodipropylamine on the top of the tower.
Example 9
(1) 133.2g of diisopropanolamine and 10.7g of catalyst A2 were charged into the autoclave and replaced 3 times with hydrogen. 136.0g of liquid ammonia was introduced, followed by hydrogen (initial pressure 1 MPa). Heating to 200 ℃ and then preserving the temperature for reaction for 4h.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa) of the filtered synthetic product, heating to 130-140 ℃, and performing reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain diaminodipropylamine on the top of the tower.
Example 10
(1) 133.2g of diisopropanolamine and 8.0g of catalyst A3 were charged into the autoclave and replaced with hydrogen 3 times. 68.0g of liquid ammonia are initially introduced and then hydrogen (initial pressure 1 MPa) is introduced. Heating to 220 ℃ and then preserving the temperature for reaction for 6h.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia from the filtered synthetic product by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa), heating to 130-140 ℃, and performing reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain diaminodipropylamine on the tower top.
Example 11
(1) 133.2g of diisopropanolamine and 9.3g of catalyst A3 were charged into the autoclave and replaced 3 times with hydrogen. 102.0g of liquid ammonia was introduced first, and then hydrogen (initial pressure 1 MPa) was introduced. Heating to 210 ℃ and then preserving the temperature for 5 hours.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa) of the filtered synthetic product, heating to 130-140 ℃, and performing reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain diaminodipropylamine on the top of the tower.
Example 12
(1) 133.2g of diisopropanolamine and 10.7g of catalyst A3 were charged into the autoclave and replaced 3 times with hydrogen. 136.0g of liquid ammonia was introduced, followed by hydrogen (initial pressure 1 MPa). Heating to 200 ℃ and then preserving the temperature for reaction for 4h.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. And (3) separating residual liquid ammonia from the filtered synthetic product by normal-temperature reduced pressure rectification (vacuum degree of minus 0.098 MPa), heating to 130-140 ℃, and performing reduced pressure rectification (vacuum degree of minus 0.098 MPa) to obtain diaminodipropylamine on the tower top.
The invention adopts gas chromatography to analyze and detect the products of the examples 4-12, and verifies the synthesis of the diaminodipropylamine.
Comparative example 1
Diaminodipropylamine is synthesized according to a preparation method in Chinese patent CN110327931B 'a catalyst and a preparation method thereof and a production process of propyleneamine using the catalyst'.
Raw materials: isopropanolamine, catalyst Co-Ni-Cu/Al 2 O 3 Specifically, the contents of the components are 0-30.0% of Co, 0-25.0% of Ni, 0-5.0% of Cu and the balance of Al 2 O 3 。
The experimental results are as follows: the synthesized product mainly contains 1, 2-propane diamine (content is more than 90 percent) and diamino dipropylamine (content is less than 2 percent).
The results of the synthesis experiments of inventive examples 4 to 12 are shown in Table 1:
TABLE 1 results for examples 4 to 12
The Ni-Co-Ce-Cr catalyst prepared by the invention has high catalytic activity, and the obtained catalyst is used for synthesizing diaminodipropylamine, the conversion rate of diisopropanolamine is more than 91%, and the selectivity of diaminodipropylamine is more than 98%. Therefore, the catalyst provided by the invention has high selectivity and high activity; the synthesis process of the diamino dipropylamine is simple, few in by-products, low in process cost, green and economic.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited to the invention itself. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The Ni-Co-Ce-Cr catalyst is characterized in that the catalyst contains 60-65% of Ni, 25-30% of Co, 5-9% of Ce and 1-5% of Cr.
2. A method of preparing the Ni-Co-Ce-Cr catalyst of claim 1, comprising the steps of:
(1) Adding an alkaline precipitator into a metal salt solution containing Ni, co, ce and Cr to completely precipitate metal ions, and aging;
(2) After aging, filtering to obtain a precipitate, washing and drying the precipitate to obtain a precursor;
(3) And roasting, grinding and activating the precursor to obtain the catalyst.
3. The preparation method according to claim 2, wherein in the step (1), the metal salt is nitrate or acetate, and the concentration of the metal salt solution is 30-50%; the alkaline precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate or ammonium bicarbonate.
4. The method according to claim 2, wherein in the step (1), the precipitation temperature is 60-80 ℃, the aging temperature is 60-80 ℃, and the aging time is 1-4 h.
5. The method according to claim 2, wherein in the step (2), the drying temperature is 80-120 ℃ and the drying time is 6-14 h.
6. The preparation method according to claim 2, wherein in the step (3), the roasting temperature is 400-500 ℃, and the roasting time is 4-8 h; the activation is carried out in the atmosphere of hydrogen, the activation temperature is 500-600 ℃, and the activation time is 3-5 h.
7. An application of a Ni-Co-Ce-Cr catalyst in the synthesis of diaminodipropylamine.
8. The use according to claim 7, wherein the synthesis of diaminodipropylamine comprises the steps of:
(1) Adding a Ni-Co-Ce-Cr catalyst and diisopropanolamine, introducing liquid ammonia and hydrogen, heating and reacting;
(2) And after the reaction is finished, cooling, filtering, recovering the catalyst, and rectifying the filtrate under reduced pressure to obtain the diaminodipropylamine.
9. The use according to claim 8, characterized in that, in the step (1), the catalyst is added in an amount of 6-8% of the mass of the diisopropanolamine, and the molar ratio of the liquid ammonia to the diisopropanolamine is (4-8) to 1,H 2 The initial pressure was 1MPa.
10. The use according to claim 8, wherein in step (1), the reaction temperature is 200-220 ℃ and the reaction time is 4-6 h.
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