CN115430456A - Catalyst for synthesizing hexamethylene diamine and preparation method and application thereof - Google Patents
Catalyst for synthesizing hexamethylene diamine and preparation method and application thereof Download PDFInfo
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- CN115430456A CN115430456A CN202211192203.6A CN202211192203A CN115430456A CN 115430456 A CN115430456 A CN 115430456A CN 202211192203 A CN202211192203 A CN 202211192203A CN 115430456 A CN115430456 A CN 115430456A
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 239000010949 copper Substances 0.000 abstract description 11
- 229910052759 nickel Inorganic materials 0.000 abstract description 11
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- UELUVOXMXAKLRG-UHFFFAOYSA-N NCCCCCC#N.C(C)O Chemical compound NCCCCCC#N.C(C)O UELUVOXMXAKLRG-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- -1 carbon phthalide chloride Chemical compound 0.000 description 2
- 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 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical class [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic chemical industry, and particularly relates to a catalyst for synthesizing hexamethylene diamine, and a preparation method and application thereof. The preparation method of the porous molecular sieve loaded copper-nickel based catalyst by adopting a coprecipitation method comprises the following steps: s1, dissolving nickel nitrate, copper nitrate and rare earth metal nitrate in water to prepare a mixed solution; and S2, placing the molecular sieve into a reactor, adding water for mixing, then simultaneously dropwise adding a precipitator and the S1 mixed solution into the reactor, stirring for reaction, adjusting the pH value of the mixture, carrying out aging reaction, carrying out suction filtration, washing and drying to obtain a precipitate, and roasting to obtain the catalyst. The copper-nickel-based catalyst prepared by the invention has the advantages that the copper can be reduced at low temperature, and the reduced copper can activate hydrogen atoms to help the reduction of nickel oxide, so that the reduction temperature of nickel is reduced. Meanwhile, the addition of rare earth metal improves the dispersion degree of metal nickel, promotes the synergistic effect between copper and nickel, and improves the integral hydrogenation effect of the catalyst.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and particularly relates to a catalyst for synthesizing hexamethylene diamine, and a preparation method and application thereof.
Background
Both amino functions of hexamethylenediamine have very high activity, which makes it possible to produce numerous chemicals as chemical intermediate. The industrial value is mainly embodied in that monomers are condensed or react with other raw materials to generate condensation products, such as nylon and nylon prepared by condensation polymerization with adipic acid or sebacic acid, and then important civil materials such as other nylon resins, nylon fibers, polyamide resin ink and the like are synthesized. Besides, the hexamethylene diamine is also widely applied to the aspects of mineral oil field demulsifiers, agricultural pesticides, building concrete additives and the like. In addition, under the irradiation of ultraviolet rays, hexamethylenediamine can react with carbon phthalide chloride to prepare 6-aminocapronitrile isocyanate, and then the polymerization reaction is continuously carried out to produce the polyurethane material, so that the polyurethane material is widely applied to the aerospace field. The application range of the hexamethylene diamine is continuously expanded, and the demand of downstream products is increasingly increased, so that the realization of industrial large-scale production of the hexamethylene diamine is the current primary task. At present, the nylon market in China is rapidly increased, and the hexamethylene diamine as the raw material gradually shows the trend of short supply and short demand, so the research and development of the novel, high-efficiency and large-scale industrial production process technology of the hexamethylene diamine are necessary.
At present, a large-scale industrialized method for synthesizing hexamethylene diamine is an adiponitrile hydrogenation method, a catalyst used in the adiponitrile hydrogenation process is mainly a Raney nickel catalyst, and the Raney nickel catalyst has poor mechanical property, is easy to break and has overhigh production cost; secondly, the catalyst has poor thermal stability, is easy to spontaneously combust in air and is difficult to store, and has great potential safety hazard in the preparation process; in addition, the catalyst has poor selectivity and low yield, and is not suitable for large-scale continuous industrial production. Therefore, the preparation of the supported catalyst which is stable, low in cost, good in hexamethylene diamine selectivity and environment-friendly has important application value and research significance.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst for synthesizing hexamethylene diamine and a preparation method and application thereof. Meanwhile, the addition of the rare earth metal improves the dispersion degree of the metal nickel, promotes the synergistic effect between the copper and the nickel, improves the integral hydrogenation effect of the catalyst, and has the advantages of simple production process, high process safety and low production cost.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of a catalyst for synthesizing hexamethylene diamine, which adopts a coprecipitation method to prepare a porous molecular sieve loaded copper-nickel-based catalyst and comprises the following steps:
s1, dissolving nickel nitrate, copper nitrate and rare earth metal nitrate in water to prepare a mixed solution;
and S2, placing the molecular sieve into a reactor, adding water for mixing, then simultaneously dropwise adding a precipitator and the mixed solution obtained in the step S1 into the reactor, stirring for reaction, adjusting the pH value of the mixture to 8 after dropwise adding, then carrying out aging reaction, carrying out suction filtration, washing and drying after the aging reaction to obtain a precipitate, and roasting to obtain the catalyst.
Preferably, the content of the copper oxide and the nickel oxide in the catalyst is 15-55% of the total mass of the catalyst, and the mass ratio of the copper oxide to the nickel oxide in the catalyst is 1.
Preferably, the content of the rare earth metal oxide is 15-45% of the total mass of the catalyst, and the rare earth metal oxide is one or more of cerium oxide, lanthanum oxide and samarium oxide.
Preferably, the porous molecular sieve is ZSM-5 or MCM-41, the pore diameter is 1-10nm, and the content of the porous molecular sieve is 25-65% of the total mass of the catalyst.
Preferably, in S1, the concentration of the metal ions in the mixed solution is 0.5-2.5mol/L.
Preferably, in S2, the molar ratio of the precipitant to the metal ion in the mixed solution is 1-3.
Preferably, in S2, the temperature of the reaction is 35-55 ℃; the time of the aging reaction is 3-8h, and the temperature is 35-55 ℃; the roasting temperature is 250-750 ℃, and the roasting time is 2.5-5.5h.
The invention also provides a catalyst prepared by the preparation method of the catalyst for synthesizing the hexamethylene diamine.
In addition, the invention also provides application of the catalyst for synthesizing the hexamethylene diamine in synthesizing the hexamethylene diamine by hydrogenating 6-aminocapronitrile, wherein the using amount of the catalyst is 1-5% of the total mass of reaction raw materials.
Preferably, the synthesis reaction is a batch kettle reaction or a fixed bed reaction, in the batch kettle reaction or the fixed bed reaction, the activation temperature of the catalyst before use is 300-450 ℃, and the space velocity of the activated hydrogen is 2000-3500h -1 The activation time is 5-10h; the temperature of the batch kettle type reaction is 120-500 ℃, and the pressure is 1.5-8.0Mpa; the temperature of the fixed bed reaction is 120-500 ℃, the pressure is 1.5-8.0Mpa, and the reaction space velocity is 0.3-3h -1 。
Compared with the prior art, the invention has the following beneficial effects:
1. the copper-nickel-based catalyst loaded on the porous molecular sieve prepared by adopting the coprecipitation method can activate hydrogen atoms and help the reduction of nickel oxide because the copper can be reduced at a low temperature, thereby reducing the reduction temperature of nickel. Meanwhile, the addition of the rare earth metal improves the dispersion degree of the metal copper and nickel, promotes the synergistic effect between the copper and the nickel, and improves the integral hydrogenation effect of the catalyst. The adopted supported metal copper nickel catalyst is cheap and easy to obtain and has long service life, and compared with a fresh catalyst, the catalyst after reduction and regeneration still maintains higher reaction activity.
2. The invention adopts the porous molecular sieve loaded copper-nickel-based catalyst prepared by a coprecipitation method for the reaction of synthesizing hexamethylene diamine by hydrogenating 6-aminocapronitrile, compared with the preparation of a Raney nickel catalyst, the selectivity of products and the conversion rate of raw materials are improved, the cost of the catalyst is low, and each component has different chemical potentials, under the action of the catalyst, each component exists in a solution in an ionic state and can be mixed more orderly, the catalyst is easy to recover, the stability is good, the production process is simple, the process safety is high, the production cost is low, the reaction conversion rate and yield are high, the purity of the hexamethylene diamine is high, no three wastes are discharged, the equipment investment is low, and the catalyst is suitable for large-scale production.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention, which will be limited only by the appended claims, wherein the various materials, reagents, instruments and equipment used in the following examples are commercially available or may be prepared by conventional methods.
Example 1
The catalyst NiCuCe/ZSM-5 prepared by adopting a coprecipitation method comprises the following steps:
s1, weighing copper nitrate, nickel nitrate and cerium nitrate with a molar ratio of 2;
s2, dissolving anhydrous sodium carbonate in water to prepare an anhydrous sodium carbonate solution with the pH value of 11, and dripping the anhydrous sodium carbonate solution and the mixed solution obtained in the S1 into a 250mL three-neck flask containing 5-10mL deionized water and 50% of ZSM-5 molecular sieve in the ratio of the total mass of the catalyst for reaction, wherein the pore diameter of the ZSM-5 molecular sieve is 6nm, the dripping speed is 1mL/min, and the molar ratio of the anhydrous sodium carbonate to metal ions in the anhydrous sodium carbonate solution is 1.2; the reaction temperature is 45 ℃ and the mixture is stirred vigorously, precipitation gradually occurs at the moment, after the dropwise addition is finished, the pH of the mixture is tested to be 6-7, and the pH of the mixture is adjusted to be 8 by using a sodium carbonate solution;
and then carrying out an aging reaction for 6 hours, keeping the constant temperature of 45 ℃ and vigorous stirring, carrying out suction filtration after the aging reaction is finished, washing and precipitating with more than 400mL of 75 ℃ deionized water until a washing liquid is neutral, then washing with more than 100mL of methanol at normal temperature in order to remove sodium ions in the precipitate as much as possible, then placing the precipitate in an electric heating forced air drying oven, drying for 10 hours at 110 ℃ to obtain a precipitate, cooling the precipitate to room temperature, grinding into powder without granular sensation by using a mortar, and roasting for 5 hours at 350 ℃ to obtain the NiCuCe/ZSM-5 catalyst.
Example 2
The catalyst NiCuLa/MCM-41 prepared by adopting a coprecipitation method comprises the following steps:
s1, weighing copper nitrate, nickel nitrate and lanthanum nitrate with the molar ratio of 2;
s2, dissolving anhydrous sodium carbonate in water to prepare an anhydrous sodium carbonate solution with the pH value of 11, and simultaneously dripping the anhydrous sodium carbonate solution and the mixed solution obtained in the S1 into a 250mL three-neck flask containing 5-10mL deionized water and 35% MCM-41 molecular sieve in the total mass of the catalyst for reaction, wherein the pore diameter of the MCM-41 molecular sieve is 6nm, the dripping speed is 1mL/min, and the molar ratio of anhydrous sodium carbonate to metal ions in the anhydrous sodium carbonate solution is 1.2; the reaction temperature is 45 ℃ and the mixture is stirred vigorously, precipitation gradually occurs at the moment, after the dropwise addition is finished, the pH of the mixture is tested to be 6-7, and the pH of the mixture is adjusted to be 8 by using a sodium carbonate solution;
and then carrying out an aging reaction for 6 hours, keeping the constant temperature of 45 ℃ and vigorous stirring, carrying out suction filtration after the aging reaction is finished, washing and precipitating with more than 400mL of 75 ℃ deionized water until a washing liquid is neutral, then washing with more than 100mL of methanol at normal temperature in order to remove sodium ions in the precipitate as much as possible, then placing the precipitate in an electric heating forced air drying oven, drying for 10 hours at 110 ℃ to obtain a precipitate, cooling the precipitate to room temperature, grinding into powder without granular sensation by using a mortar, and roasting for 5 hours at 450 ℃ to obtain the NiCuLa/MCM-41 catalyst.
The pore structure performance of the catalyst of example 1-2 was calculated by the BET method, and the specific surface areas of the NiCuCe/ZSM-5 and NiCuLa/MCM-41 catalysts prepared in example 1-2 were 200-300m 2 Between/g, pore volume and pore diameter are respectively 0.5-1.0cm 3 Between/g and 4-5 nm.
Example 3
A method for preparing hexamethylene diamine by hydrogenating 6-aminocapronitrile comprises the following steps:
adding a 20 percent ethanol solution of 6-aminocapronitrile into a batch kettle type reaction kettle, heating and activating 20g (about 25 mL) of NiCuCe/ZSM-5 catalyst prepared in example 1 by hydrogen in a fixed bed at the temperature of 350 ℃ and the space velocity of the activated hydrogen of 2500h -1 Activating for 6h; then transferring the mixture into an intermittent kettle type reaction kettle under the protection of nitrogen, sealing the reaction kettle, replacing air in the reaction kettle with hydrogen, setting the reaction temperature of the reaction kettle to be 180 ℃, and filling hydrogen to the set reaction pressure of 6MPa; and when the reaction temperature reaches 180 ℃, starting stirring and timing, keeping the stirring speed at 600r/min, after reacting for 3 hours, closing the stirring and heating device, cooling the reaction kettle to room temperature, releasing pressure to normal pressure, taking the mixture after reaction, and analyzing the conversion rate by chromatography to be 99% and the selectivity of the hexamethylene diamine to be 99.5%. And distilling and refining under reduced pressure to obtain the high-purity hexamethylene diamine.
Example 4
A method for preparing hexamethylene diamine by hydrogenating 6-aminocapronitrile comprises the following steps:
adding a 30% mass fraction 6-aminocapronitrile ethanol solution into a batch kettle type reaction kettle, and catalyzing the reduced NiCuCe/ZSM-5 prepared in example 1Adding 20g (about 25 mL) of the agent into a batch kettle type reaction kettle, sealing, replacing the air in the kettle with hydrogen, heating and activating the catalyst at the temperature of 350 ℃ and the space velocity of the activated hydrogen of 2500h -1 And the activation time is 6h. After the catalyst is activated, the temperature of the reaction kettle is reduced to 180 ℃, hydrogen is filled to the set reaction pressure of 6MPa, when the reaction temperature reaches 180 ℃, stirring is started and timing is started, the rotating speed of the stirring is kept at 600r/min, after 4.5 hours of reaction, a stirring and heating device is closed, the reaction kettle is cooled to room temperature, pressure is relieved to normal pressure, the mixture after the reaction is taken out, the conversion rate is 99% through chromatographic analysis, and the selectivity of hexamethylene diamine is 99.5%. And distilling and refining under reduced pressure to obtain the high-purity hexamethylene diamine.
Example 5
A method for preparing hexamethylene diamine by hydrogenating 6-aminocapronitrile comprises the following steps:
5% by weight of 6-aminocapronitrile ethanol solution was charged into a batch kettle reactor, and 20g (about 25 mL) of the NiCuLa/MCM-41 catalyst prepared in example 2 was activated by heating with hydrogen in a fixed bed at a temperature of 380 ℃ for activation and a space velocity of 2500h for activated hydrogen -1 Activation time is 8h; then transferring the mixture into an intermittent kettle type reaction kettle under the protection of nitrogen, sealing the reaction kettle, replacing air in the reaction kettle with hydrogen, setting the reaction temperature of the reaction kettle to be 180 ℃, and filling hydrogen to the set reaction pressure of 6MPa; and when the reaction temperature reaches 180 ℃, starting stirring and timing, keeping the stirring rotation speed at 600r/min, after reacting for 1h, closing the stirring and heating device, cooling the reaction kettle to room temperature, relieving pressure to normal pressure, taking the mixture after reaction, and analyzing the conversion rate by chromatography to be 98% and the selectivity of the hexamethylene diamine to be 99.5%. And distilling and refining under reduced pressure to obtain the high-purity hexamethylene diamine.
Example 6
Adding 75 percent by mass of 6-aminocapronitrile ethanol solution into a batch kettle type reaction kettle, heating and activating 20g (about 25 mL) of NiCuCe/ZSM-5 catalyst prepared in example 1 in a fixed bed by using hydrogen, wherein the activation temperature of the catalyst is 350 ℃, and the space velocity of the activated hydrogen is 2500h -1 Activating for 6 hours, then transferring the mixture into a batch kettle type reaction kettle under the protection of nitrogen, and carrying outAfter sealing, replacing the air in the reaction kettle with hydrogen, setting the reaction temperature of the reaction kettle to be 180 ℃, and filling hydrogen to the set reaction pressure of 6MPa; and when the reaction temperature reaches 180 ℃, starting stirring and timing, keeping the stirring rotation speed at 600r/min, after 8 hours of reaction, closing the stirring and heating device, cooling the reaction kettle to room temperature, relieving pressure to normal pressure, taking the mixture after the reaction, and analyzing the conversion rate by chromatography to be 95% and the selectivity of the hexamethylene diamine to be 98.5%. And distilling and refining under reduced pressure to obtain the high-purity hexamethylene diamine.
Example 7
20g (about 25 mL) of the NiCuCe/ZSM-5 catalyst prepared in example 1 was charged to a fixed bed reactor. The catalyst is used after being activated by hydrogen, the activation temperature is 320 ℃, the temperature is programmed to rise for 1h and reaches the activation temperature from room temperature, and the airspeed of the activated hydrogen is 2500h -1 And activating for 8 hours. After the catalyst is activated, the temperature of a bed layer is reduced to 180 ℃, the pressure of a system is increased to 5MPa, and a 6-aminocapronitrile ethanol solution with the mass fraction of 20 percent is pumped into the reaction system at the airspeed of 1h -1 . The reaction mixture was taken and analyzed by chromatography for conversion of 97% and selectivity to hexamethylene diamine of 99.5%. And distilling and refining under reduced pressure to obtain the high-purity hexamethylene diamine.
Comparative example 1
The process for preparing hexamethylenediamine by hydrogenating 6-aminocapronitrile is the same as in example 3, except that a Raney nickel catalyst is used as the catalyst. The reaction mixture was taken and chromatographed with a conversion of 92% and hexamethylenediamine selectivity of 95.3%. And distilling and refining under reduced pressure to obtain the high-purity hexamethylene diamine.
In conclusion, the copper-nickel-based catalyst loaded on the porous molecular sieve prepared by adopting the coprecipitation method has the advantages that the copper can be reduced at a low temperature, and the reduced copper can activate hydrogen atoms to help the reduction of nickel oxide, so that the reduction temperature of nickel is reduced. Meanwhile, the addition of the rare earth metal improves the dispersion degree of the copper and the nickel, promotes the synergistic effect between the copper and the nickel, improves the overall hydrogenation effect of the catalyst, is used for the reaction of synthesizing the hexamethylene diamine by hydrogenating 6-aminocapronitrile, and has high reaction conversion rate, high yield and high purity of the hexamethylene diamine. Compared with the preparation of the Raney nickel catalyst, the catalyst prepared by the method has low cost, each component has different chemical potentials, and under the action of the catalyst, each component exists in the solution in an ion form and can be mixed more orderly, the production process is simple, the process safety is high, the production cost is low, no three wastes are discharged, the equipment investment is low, and the method is suitable for large-scale production.
It should be noted that, when the present invention relates to a numerical range, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of a catalyst for synthesizing hexamethylene diamine is characterized in that a coprecipitation method is adopted to prepare a porous molecular sieve loaded copper-nickel-based catalyst, and comprises the following steps:
s1, dissolving nickel nitrate, copper nitrate and rare earth metal nitrate in water to prepare a mixed solution;
and S2, placing the molecular sieve in a reactor, adding water for mixing, then simultaneously dropwise adding a precipitator and the mixed solution obtained in the S1 into the reactor, stirring for reaction, adjusting the pH of the mixture to 8 after the dropwise addition is finished, then carrying out an aging reaction, carrying out suction filtration, washing and drying after the aging reaction is finished to obtain a precipitate, and roasting to obtain the catalyst.
2. The method for preparing a catalyst for synthesizing hexamethylenediamine according to claim 1, wherein the content of copper oxide and nickel oxide in the catalyst is 15 to 55% by mass of the total mass of the catalyst, and the mass ratio of copper oxide to nickel oxide in the catalyst is 1.
3. The method for preparing a catalyst for synthesizing hexamethylene diamine according to claim 1, wherein the content of the rare earth metal oxide is 15-45% of the total mass of the catalyst, and the rare earth metal oxide is one or more of cerium oxide and lanthanum oxide.
4. The method for preparing a catalyst for the synthesis of hexamethylenediamine according to claim 1, wherein the porous molecular sieve is ZSM-5 or MCM-41, the pore size is 1 to 10nm, and the content of the porous molecular sieve is 25 to 65% of the total mass of the catalyst.
5. The method of producing a hexamethylenediamine catalyst according to claim 1, wherein the concentration of the metal ion in the mixed solution in S1 is 0.5 to 2.5mol/L.
6. The method for preparing a catalyst for synthesizing hexamethylenediamine according to claim 1, wherein in S2, the molar ratio of the precipitant to the metal ion in the mixed solution is 1 to 3, and the precipitant is an aqueous ammonia solution having a pH =11, a sodium carbonate solution, or a sodium bicarbonate solution.
7. The method for preparing a catalyst for synthesizing hexamethylenediamine according to claim 1, wherein the reaction temperature in S2 is 35 to 55 ℃; the aging reaction time is 3-8h, and the temperature is 35-55 ℃; the roasting temperature is 250-750 ℃, and the roasting time is 2.5-5.5h.
8. A catalyst produced by the method for producing a catalyst for synthesizing hexamethylenediamine according to any one of claims 1 to 7.
9. Use of the catalyst according to claim 8 for the hydrogenation of 6-aminocapronitrile to hexamethylenediamine, wherein the amount of the catalyst is 1-5% of the total mass of the reaction raw materials.
10. The use of the catalyst according to claim 9 in the synthesis of hexamethylenediamine by hydrogenation of 6-aminocapronitrile, wherein the synthesis reaction is a batch tank reaction or a fixed bed reaction, and in the batch tank reaction or the fixed bed reaction, the catalyst is activated at 300-450 ℃ before use and at a space velocity of 2000-3500h -1 The activation time is 5-10h; the temperature of the batch kettle type reaction is 120-500 ℃, and the pressure is 1.5-8.0Mpa; the temperature of the fixed bed reaction is 120-500 ℃, the pressure is 1.5-8.0Mpa, and the reaction space velocity is 0.3-3h -1 。
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| CN104923240A (en) * | 2015-06-03 | 2015-09-23 | 湘潭大学 | Sepiolite-loaded nickel-based catalyst modified by two metals, as well as preparation method and application of sepiolite-loaded nickel-based catalyst |
| CN107159308A (en) * | 2017-06-22 | 2017-09-15 | 中国天辰工程有限公司 | A kind of Ni-based molecular sieve catalyst and preparation method thereof |
| CN109647419A (en) * | 2018-12-20 | 2019-04-19 | 大连理工大学 | A kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, preparation method and application |
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| CN104923240A (en) * | 2015-06-03 | 2015-09-23 | 湘潭大学 | Sepiolite-loaded nickel-based catalyst modified by two metals, as well as preparation method and application of sepiolite-loaded nickel-based catalyst |
| CN107159308A (en) * | 2017-06-22 | 2017-09-15 | 中国天辰工程有限公司 | A kind of Ni-based molecular sieve catalyst and preparation method thereof |
| CN109647419A (en) * | 2018-12-20 | 2019-04-19 | 大连理工大学 | A kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, preparation method and application |
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