CN115869960B - 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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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- KHURTEAYLZEQHD-UHFFFAOYSA-N 3-n-propylpropane-1,1,3-triamine Chemical compound CCCNCCC(N)N KHURTEAYLZEQHD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 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 16
- 238000001914 filtration Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 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
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 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
- 238000000227 grinding Methods 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
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 22
- 239000011651 chromium Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 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
- 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
- AMLFJZRZIOZGPW-NSCUHMNNSA-N (e)-prop-1-en-1-amine Chemical compound C\C=C\N AMLFJZRZIOZGPW-NSCUHMNNSA-N 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 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
- 239000000463 material Substances 0.000 description 2
- 238000001228 spectrum 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229940102253 isopropanolamine Drugs 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
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (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 has the Ni content of 60-65%, the Co content of 25-30%, the Ce content of 5-9% and the Cr content of 1-5%. The Ni-Co-Ce-Cr catalyst has high catalytic activity, and the catalyst obtained by the method is used for synthesizing diaminodipropylamine and has excellent activity and selectivity. The synthesis process of the diaminodipropylamine 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
The diaminodipropylamine, which is also called as dipropylenetriamine, is used as an epoxy curing agent, an emulsifying agent, an insecticide and the like, can be used for synthesizing biological adsorption separation materials and various surfactants, and is also an important chemical intermediate for manufacturing dye and rubber. Early curatives and the like used more diethylenetriamine and are now increasingly replaced by dipropylenetriamine.
Chinese patent CN110327931B provides a catalyst, a preparation method thereof and a process for producing propylene amine using the catalyst. The patent synthesizes a series of propylene amine products, such as 1, 2-propylene diamine, dimethyl piperazine, diamino dipropylamine, polypropylene polyamine and the like, by taking monoisopropanolamine as a raw material. The catalyst is Co-Ni-Cu/Al 2O3, the content of each component is Co 0-30.0%, ni 0-25.0%, cu 0-5.0% and the balance Al 2O3. The synthesized product is mainly 1, 2-propylene diamine (the content is more than 90 percent), and diaminodipropylamine is relatively less (the content is more than 2 percent). The catalyst and the synthesis process method are suitable for the synthesis production of 1, 2-propylene diamine, have extremely poor selectivity to diaminodipropylamine, and are not suitable for the industrial production of diaminodipropylamine.
Disclosure of Invention
The invention aims to: the invention aims at overcoming the defects of the prior art and provides a Ni-Co-Ce-Cr catalyst and a preparation method and application thereof. The Ni-Co-Ce-Cr catalyst prepared by the invention has high catalytic activity, and the catalyst obtained by the invention is used for synthesizing diaminodipropylamine and has excellent activity and selectivity.
The technical scheme is as follows: the aim of the invention is achieved by the following technical scheme:
the invention provides a Ni-Co-Ce-Cr catalyst, wherein the Ni content of the catalyst is 60-65%, the Co content is 25-30%, the Ce content is 5-9%, and the Cr content is 1-5%.
Experiments show that under the limitation of the content proportion of each component, the catalytic function of the catalyst can be maximized, especially the addition of Ce can effectively improve the activity of the catalyst and 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 precipitant into the Ni, co, ce, cr-containing metal salt solution according to a certain proportion to completely precipitate metal ions, and aging;
(2) Filtering to obtain a precipitate after aging, washing and drying the precipitate to obtain a precursor;
(3) And roasting, grinding and activating the precursor to obtain the catalyst.
In a specific implementation mode of the invention, the step (1) is that Ni, co, ce, cr of metal salt is added into water according to a proportion, and dissolved at 60-80 ℃ to prepare metal salt solution; then, maintaining the temperature of the metal salt solution, dropping an alkaline precipitant solution with a mass concentration of 40% into the metal salt solution, and aging after the dropping 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 precipitant 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 are added to be matched with Ni, so that the overall activity of the catalyst is improved. Experiments show that the method of coprecipitation can greatly improve the catalytic effect of the nickel-based catalyst, and can further improve the catalytic effect of the catalyst and enhance the activity and selectivity of the catalyst after Co, ce and Cr are added.
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, i.e., aging and precipitation are completed at the same temperature. The purpose of aging is to allow the precipitated particles to grow up and to perfect or transform the crystal form. In the invention, the specific process of ageing the precipitate is not particularly required, and the unconfined condition can be finished by adopting the conventional technology.
Under the above conditions, the nucleation rate and growth rate can be effectively controlled, thereby obtaining a proper crystal structure. Provides a good foundation for subsequent roasting, and ensures that the roasted material has a large number of tiny pore canals 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 methods well known in the art may be employed.
Preferably, in the step (3), the roasting temperature is 400-500 ℃ and the roasting time is 4-8 hours; 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, each component 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 roasting temperature is too low to decompose the metal hydroxide. In the roasting temperature and the roasting time, each component in the precursor can be completely oxidized, impurities such as chemically bound 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; too low an activation temperature or too short a time does not allow the metal oxide to be reduced. In the activation temperature and activation time, the nickel oxide can be completely reduced to metallic nickel without influencing the catalyst structure.
The invention also provides an application of the Ni-Co-Ce-Cr catalyst in 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 carrying out reaction;
(2) After the reaction is finished, cooling, filtering, recovering the catalyst, and rectifying the filtrate under reduced pressure to obtain the diaminodipropylamine.
One embodiment of the invention for synthesizing diaminodipropylamine is: the Ni-Co-Ce-Cr catalyst and diisopropanolamine were added to the autoclave and replaced with hydrogen. Liquid ammonia is introduced first, and then hydrogen is introduced. After heating, the reaction is carried out at a constant temperature. After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa) to obtain diaminodipropylamine.
Preferably, in order to ensure that the reaction proceeds smoothly, the catalyst is added in the step (1) in an amount of 6 to 8% by mass of diisopropanolamine, the molar ratio of liquid ammonia to diisopropanolamine is (4 to 8): 1, and the initial pressure of H 2 is 1MPa.
The catalyst is used in the proportion, so that the smooth reaction and the selectivity of the reaction can be ensured. When the catalyst dosage is smaller, the catalytic effect is poorer, and the conversion rate of diisopropanolamine is lower; excessive catalyst usage increases costs and increases difficulty in recovery processing of the catalyst.
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 raw materials is low; too high a temperature may lead to an increase in side reactions. The reaction time is too long, the conversion rate and the yield are not greatly affected, but the working hours and the energy consumption are increased.
The beneficial effects are that:
The Ni-Co-Ce-Cr catalyst prepared by the invention has high catalytic activity, and the catalyst obtained by the invention is used for synthesizing diaminodipropylamine and has excellent activity and selectivity. The invention adopts diisopropanolamine as raw material to synthesize diaminodipropylamine, shortens the reaction flow and reduces the generation of byproducts. Therefore, the catalyst and the synthesis process of the diaminodipropylamine provided by the invention have the advantages of high selectivity, high activity, few byproducts, simple synthesis process, low process cost, green and economy.
Drawings
FIG. 1 is a gas spectrum of a diaminodipropylamine standard;
FIG. 2 is a gas chart of diaminodipropylamine synthesized in example 4.
Detailed Description
The technical scheme of the present invention is described in detail below through 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) Nickel acetate, cobalt nitrate, cerium nitrate and chromium nitrate are added into water according to the proportion of 60% of Ni, 30% of Co, 9% of Ce and 1% of Cr, heated to 60 ℃, stirred and dissolved to prepare a metal salt solution with the mass fraction of 30%. At 60 ℃, 60% sodium hydroxide solution by mass is added to completely precipitate the metal ions, and the mixture is aged at that temperature for 4 hours.
(2) After aging, the precipitate was filtered, washed several times with water and ethanol, and dried at 80 ℃ for 14h to obtain a catalyst precursor.
(3) The dried precursor is baked for 8 hours at 400 ℃, and the baked metal oxide is ground to 80 meshes and sieved. And activating for 5 hours at 500 ℃ under the atmosphere of hydrogen to obtain the catalyst A1.
EXAMPLE 2 preparation of Ni-Co-Ce-Cr catalyst
(1) Nickel acetate, cobalt nitrate, cerium nitrate and chromium nitrate are added into water according to the proportion of 62% of Ni, 28% of Co, 7% of Ce and 3% of Cr, and are heated to 70 ℃, stirred and dissolved to prepare a metal salt solution with the mass fraction of 40%. At 70 ℃, 50% by mass of potassium hydroxide solution was added to completely precipitate the metal ions, and the mixture was aged at this temperature for 2 hours.
(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) The dried precursor is baked for 6 hours at 450 ℃, and the baked metal oxide is ground to 80 meshes and sieved. And activating for 4 hours under the condition of 550 ℃ in the atmosphere of hydrogen to obtain the catalyst A2.
EXAMPLE 3 preparation of Ni-Co-Ce-Cr catalyst
(1) Nickel acetate, cobalt nitrate, cerium nitrate and chromium nitrate are added into water according to the proportion of 65% of Ni, 25% of Co, 5% of Ce and 5% of Cr, heated to 80 ℃, stirred and dissolved to prepare a metal salt solution with the mass fraction of 50%. At 80 ℃, a 40% mass fraction sodium carbonate solution was added to completely precipitate the metal ions, and the mixture was aged at this temperature for 1h.
(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) The dried precursor is baked for 4 hours at 500 ℃, and the baked metal oxide is ground to 80 meshes and sieved. And activating for 3 hours at 600 ℃ in the atmosphere of hydrogen to obtain the catalyst A3.
The catalyst is prepared by adopting a coprecipitation method, and the metal elements and the proportion are fixed, so that the problem of unadsorbed metal elements is avoided. The performance of the catalyst of the invention adopts the synthesis experiment of diaminodipropylamine to verify the effect, and the catalyst composition 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 introduced into the autoclave and replaced 3 times with hydrogen. 68.0g of liquid ammonia is introduced first, followed by hydrogen (initial pressure 1 MPa). Heating to 220 ℃, and then preserving heat for reaction for 6h.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa), and diaminodipropylamine is obtained at the top of the tower.
FIG. 1 is a gas spectrum of a diaminodipropylamine standard;
FIG. 2 is a gas chart of diaminodipropylamine synthesized in example 4;
Diaminodipropylamine standard: alatin reagent cat# D155042
Gas chromatography instrument: agilent 7820A gas chromatograph
By contrast with a standard substance gas spectrogram, the synthesis method provided by the invention is verified to be effective in synthesizing diaminodipropylamine.
EXAMPLE 5 Synthesis of diaminodipropylamine
(1) 133.2G of diisopropanolamine and 9.3g of catalyst A1 were introduced into the autoclave and replaced 3 times with hydrogen. 102.0g of liquid ammonia is introduced first, followed by hydrogen (initial pressure 1 MPa). Heating to 210 ℃, and then preserving heat for reaction for 5 hours.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa), and diaminodipropylamine is obtained at the top of the tower.
EXAMPLE 6 Synthesis of diaminodipropylamine
(1) 133.2G of diisopropanolamine and 10.7g of catalyst A1 were introduced into the autoclave and replaced 3 times with hydrogen. 136.0g of liquid ammonia is introduced first, followed by hydrogen (initial pressure 1 MPa). Heating to 200 ℃, and then preserving heat for reaction for 4 hours.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa), and diaminodipropylamine is obtained at the top of the tower.
Example 7
(1) 133.2G of diisopropanolamine and 8.0g of catalyst A2 were introduced into the autoclave and replaced 3 times with hydrogen. 68.0g of liquid ammonia is introduced first, followed by hydrogen (initial pressure 1 MPa). Heating to 220 ℃, and then preserving heat for reaction for 6h.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa), and diaminodipropylamine is obtained at the top of the tower.
Example 8
(1) 133.2G of diisopropanolamine and 9.3g of catalyst A2 were introduced into the autoclave and replaced 3 times with hydrogen. 102.0g of liquid ammonia is introduced first, followed by hydrogen (initial pressure 1 MPa). Heating to 210 ℃, and then preserving heat for reaction for 5 hours.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa), and diaminodipropylamine is obtained at the top of the tower.
Example 9
(1) 133.2G of diisopropanolamine and 10.7g of catalyst A2 were introduced into the autoclave and replaced 3 times with hydrogen. 136.0g of liquid ammonia is introduced first, followed by hydrogen (initial pressure 1 MPa). Heating to 200 ℃, and then preserving heat for reaction for 4 hours.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa), and diaminodipropylamine is obtained at the top of the tower.
Example 10
(1) 133.2G of diisopropanolamine and 8.0g of catalyst A3 were introduced into the autoclave and replaced 3 times with hydrogen. 68.0g of liquid ammonia is introduced first, followed by hydrogen (initial pressure 1 MPa). Heating to 220 ℃, and then preserving heat for reaction for 6h.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa), and diaminodipropylamine is obtained at the top of the tower.
Example 11
(1) 133.2G of diisopropanolamine and 9.3g of catalyst A3 were introduced into the autoclave and replaced 3 times with hydrogen. 102.0g of liquid ammonia is introduced first, followed by hydrogen (initial pressure 1 MPa). Heating to 210 ℃, and then preserving heat for reaction for 5 hours.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa), and diaminodipropylamine is obtained at the top of the tower.
Example 12
(1) 133.2G of diisopropanolamine and 10.7g of catalyst A3 were introduced into the autoclave and replaced 3 times with hydrogen. 136.0g of liquid ammonia is introduced first, followed by hydrogen (initial pressure 1 MPa). Heating to 200 ℃, and then preserving heat for reaction for 4 hours.
(2) After the reaction is finished, cooling, decompressing and filtering, wherein the catalyst is recycled. The filtered synthesized product is subjected to normal temperature vacuum rectification (vacuum degree-0.098 MPa) to separate residual liquid ammonia, and then is heated to 130-140 ℃ for vacuum rectification (vacuum degree-0.098 MPa), and diaminodipropylamine is obtained at the top of the tower.
The invention adopts gas chromatography to analyze and detect the products of examples 4-12, and verifies the synthesis of diaminodipropylamine.
Comparative example 1
According to the preparation method in China patent CN110327931B 'a catalyst and a preparation method thereof and a propylene amine production process applying the catalyst', diaminodipropylamine is synthesized.
Raw materials: the isopropanolamine catalyst Co-Ni-Cu/Al 2O3 contains Co 0-30.0 wt%, ni 0-25.0 wt%, cu 0-5.0 wt% and Al 2O3 for the rest.
Experimental results: the synthesized product is mainly 1, 2-propylene diamine (content > 90%), diaminodipropylamine (content < 2%).
The results of the synthesis experiments of examples 4 to 12 of the present invention 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, 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 diaminodipropylamine is simple, few in byproducts, low in process cost, green and economic.
As described above, although the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limiting the invention itself. Various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the Ni-Co-Ce-Cr catalyst is characterized by comprising the following steps of:
(1) Adding an alkaline precipitant into the Ni, co, ce, cr-containing metal salt solution to completely precipitate metal ions, and aging;
(2) Filtering to obtain a precipitate after aging, washing and drying the precipitate to obtain a precursor;
(3) Roasting, grinding and activating the precursor to obtain the catalyst;
the activation is carried out in the atmosphere of hydrogen, the activation temperature is 500-600 ℃, and the activation time is 3-5 h;
the catalyst comprises 60-65% of Ni, 25-30% of Co, 5-9% of Ce and 1-5% of Cr.
2. The preparation method of claim 1, 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.
3. The method according to claim 1, wherein in the step (1), the temperature of the precipitation is 60-80 ℃, the aging temperature is 60-80 ℃, and the aging time is 1-4 hours.
4. The method according to claim 1, wherein in the step (2), the drying temperature is 80-120 ℃ and the drying time is 6-14 h.
5. The method according to claim 1, wherein in the step (3), the baking temperature is 400-500 ℃ and the baking time is 4-8 hours.
6. A Ni-Co-Ce-Cr catalyst prepared by the preparation method according to any one of claims 1 to 5.
7. Use of a Ni-Co-Ce-Cr catalyst of claim 6 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 carrying out reaction;
(2) 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, wherein in the step (1), the catalyst is added in an amount of 6-8% by mass of diisopropanolamine, the molar ratio of liquid ammonia to diisopropanolamine is (4-8): 1, and the initial pressure of h 2 is 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 hours.
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