CN115430456B - Catalyst for synthesizing hexamethylenediamine and preparation method and application thereof - Google Patents
Catalyst for synthesizing hexamethylenediamine and preparation method and application thereof Download PDFInfo
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- CN115430456B CN115430456B CN202211192203.6A CN202211192203A CN115430456B CN 115430456 B CN115430456 B CN 115430456B CN 202211192203 A CN202211192203 A CN 202211192203A CN 115430456 B CN115430456 B CN 115430456B
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 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
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 11
- 239000000203 mixture 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
- 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 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 7
- 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 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 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 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 20
- 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 9
- 230000009467 reduction Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 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
- 238000001914 filtration Methods 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 239000013049 sediment Substances 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
- 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
- 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 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 230000004075 alteration Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 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 2
- 238000011031 large-scale manufacturing process 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
- 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
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- -1 6-aminocapronitrile isocyanate Chemical compound 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 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
- 238000001308 synthesis method Methods 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)
- Crystallography & Structural Chemistry (AREA)
- Dispersion 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 hexamethylenediamine, and a preparation method and application thereof. The method for preparing the porous molecular sieve supported copper-nickel-based catalyst by adopting the coprecipitation method comprises the following steps: s1, dissolving nickel nitrate, copper nitrate and rare earth metal nitrate in water to prepare a mixed solution; s2, placing the molecular sieve in a reactor, adding water for mixing, then simultaneously dripping a precipitator and the S1 mixed solution into the reactor, stirring for reaction, adjusting the pH value of the mixture, performing aging reaction, filtering, washing, drying to obtain a precipitate, and roasting to obtain the catalyst. The copper-nickel-based catalyst prepared by the invention 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 dispersity of metallic nickel, promotes the synergistic effect between copper and nickel and improves the hydrogenation effect of the whole catalyst.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and particularly relates to a catalyst for synthesizing hexamethylenediamine, and a preparation method and application thereof.
Background
Both amino functions of hexamethylenediamine are extremely active, which enables them to be used as chemical intermediates for the production of numerous chemicals. The industrial value is mainly reflected in that the monomer is condensed or reacts with other raw materials to generate condensation products, such as condensation polymerization with adipic acid or sebacic acid to prepare nylon and nylon, and then other important civil materials such as nylon resin, nylon fiber, polyamide resin ink and the like are synthesized. In addition, hexamethylenediamine is widely applied to 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 phthalein chloride to prepare 6-aminocapronitrile isocyanate, and then the polyurethane material produced by the polymerization reaction is continuously polymerized, so that the polyurethane material is widely applied to the field of aerospace. The application range of hexamethylenediamine is continuously expanded, and the demand of downstream products is increasingly increased, so that the realization of industrial mass production of hexamethylenediamine is a primary task at present. At present, the nylon market in China is rapidly growing, and raw material hexamethylenediamine gradually shows a tendency of supply and demand, so that research and development of novel, efficient and large-scale industrial production process technology of hexamethylenediamine are very necessary.
At present, the large-scale industrialized hexamethylenediamine synthesis method is an adiponitrile hydrogenation method, the catalyst used in the adiponitrile hydrogenation process is mainly a Raney nickel catalyst, the Raney nickel catalyst has poor mechanical properties, is easy to crush and has high production cost; secondly, the catalyst has poor thermal stability, is easy to self-ignite in air, is not easy 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 supported catalyst which is stable in development, low in cost, good in hexamethylenediamine 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 hexamethylenediamine, a preparation method and application thereof, and a porous molecular sieve supported copper-nickel-based catalyst prepared by adopting a coprecipitation method. Meanwhile, the addition of rare earth metal improves the dispersity of metallic nickel, promotes the synergistic effect between copper and nickel, improves the hydrogenation effect of the whole catalyst, and has simple production process, high process safety and low production cost.
The invention solves the technical problems through the following technical proposal.
The invention provides a preparation method of a catalyst for synthesizing hexamethylenediamine, which adopts a coprecipitation method to prepare a copper-nickel-based catalyst loaded by a porous molecular sieve, and comprises the following steps:
s1, dissolving nickel nitrate, copper nitrate and rare earth metal nitrate in water to prepare a mixed solution;
s2, placing the molecular sieve in a reactor, adding water for mixing, then simultaneously dripping the 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 dripping, then carrying out 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.
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 1:1-1.5.
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 metal ions in the mixed solution is 0.5-2.5mol/L.
Preferably, in S2, the molar ratio of the precipitant to the metal ions in the mixed solution is 1-3:1, and the precipitant is aqueous ammonia, sodium carbonate solution or sodium bicarbonate solution with ph=11.
Preferably, in S2, the temperature of the reaction is 35-55 ℃; 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.
The invention also provides a catalyst prepared by the preparation method of the catalyst for synthesizing hexamethylenediamine.
In addition, the invention also provides application of the catalyst for synthesizing hexamethylenediamine in hydrogenation of 6-aminocapronitrile, wherein the dosage of the catalyst is 1-5% of the total mass of reaction raw materials.
Preferably, the synthesis reaction is batch kettle reaction or fixed bed reaction, in which the activation temperature of the catalyst is 300-450 ℃ before use and the space velocity of the activated hydrogen is 2000-3500h -1 The activation time is 5-10h; the temperature of the batch kettle 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 porous molecular sieve supported copper-nickel-based catalyst prepared by adopting the coprecipitation method is characterized in that 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 dispersity of copper and nickel, promotes the synergistic effect between copper and nickel and improves the hydrogenation effect of the whole catalyst. The adopted supported metal copper-nickel catalyst is cheap and easy to obtain, has long service life, and still maintains higher reaction activity after reduction and regeneration compared with a fresh catalyst.
2. Compared with the preparation of Raney nickel catalyst, the catalyst has the advantages of improved selectivity to products and conversion rate of raw materials, low cost, different chemical potentials of the components, more orderly mixing of the components in ionic form in solution under the action of the catalyst, easy recovery of the catalyst, good stability, simple production process, high process safety, low production cost, high reaction conversion rate and yield, high purity of hexamethylenediamine, no three-waste emission and low equipment investment, and is suitable for large-scale production.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the technical terms used in the present invention are only for describing specific embodiments, and are not intended to limit the scope of the present invention, and various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention may be purchased commercially or prepared by existing methods unless otherwise specifically described.
Example 1
The catalyst NiCuCe/ZSM-5 prepared by adopting the coprecipitation method comprises the following steps:
s1, weighing copper nitrate, nickel nitrate and cerium nitrate with a molar ratio of 2:2:1, and dissolving the copper nitrate, the nickel nitrate and the cerium nitrate in deionized water to prepare a mixed solution with a metal ion concentration of 1 mol/L;
s2, dissolving anhydrous sodium carbonate into water to prepare an anhydrous sodium carbonate solution with pH of 11, simultaneously dripping the anhydrous sodium carbonate solution and the mixed solution obtained in the S1 into a 250mL three-neck flask filled with 5-10mL deionized water and ZSM-5 molecular sieve accounting for 50% of the total mass of the catalyst for reaction, wherein the aperture 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 1:1.2; the reaction temperature was 45 ℃ and stirring was vigorous, at which time precipitation gradually occurred, and after the end of the dropwise addition, the pH of the test mixture was adjusted to pH 8 with sodium carbonate solution=6-7;
then aging reaction is carried out for 6 hours, the constant temperature is kept at 45 ℃ and the stirring is violent, suction filtration is carried out after the aging reaction is finished, washing precipitation is carried out with more than 400mL of deionized water at 75 ℃ until washing liquid is neutral, washing with more than 100mL of methanol at normal temperature is carried out, the purpose is to remove sodium ions in the precipitation as much as possible, then the precipitation is placed in an electrothermal blowing drying oven, drying is carried out for 10 hours at 110 ℃ to obtain the precipitation, after the precipitation is cooled to room temperature, the precipitation is ground into powder without granular sensation by a mortar, and roasting is carried out 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 a molar ratio of 2:2:1, and dissolving the copper nitrate, the nickel nitrate and the lanthanum nitrate in deionized water to prepare a mixed solution with a metal ion concentration of 2 mol/L;
s2, dissolving anhydrous sodium carbonate into water to prepare an anhydrous sodium carbonate solution with pH of 11, simultaneously dripping the anhydrous sodium carbonate solution and the mixed solution obtained in the S1 into a 250mL three-neck flask filled with 5-10mL deionized water and an MCM-41 molecular sieve accounting for 35% of the total mass of the catalyst for reaction, wherein the aperture of the MCM-41 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 1:1.2; the reaction temperature was 45 ℃ and stirring was vigorous, at which time precipitation gradually occurred, and after the end of the dropwise addition, the pH of the test mixture was adjusted to pH 8 with sodium carbonate solution=6-7;
then aging reaction is carried out for 6 hours, the constant temperature is kept at 45 ℃ and the stirring is violent, suction filtration is carried out after the aging reaction is finished, washing sediment with more than 400mL of deionized water at 75 ℃ is carried out until the washing liquid is neutral, then washing with more than 100mL of methanol at normal temperature is carried out, the purpose is to remove sodium ions in the sediment as much as possible, then the sediment is placed in an electrothermal blowing drying oven, drying is carried out for 10 hours at 110 ℃ to obtain the sediment, after the sediment is cooled to the room temperature, the sediment is ground into powder without granular sensation by a mortar, and roasting is carried out for 5 hours at 450 ℃ to obtain the NiCuLa/MCM-41 catalyst.
The BET method is used for calculating the pore structure performance of the catalysts of examples 1-2, and the specific surface area of the NiCuCe/ZSM-5 and NiCuLa/MCM-41 catalysts prepared in examples 1-2 is 200-300m 2 Between/g, pore volume and pore diameter are respectively 0.5-1.0cm 3 And/g and 4-5 nm.
Example 3
A process for the preparation of hexamethylenediamine by hydrogenation of 6-aminocapronitrile comprising the steps of:
adding 20% 6-aminocapronitrile ethanol solution into a batch kettle reaction kettle, heating and activating 20g (about 25 mL) of NiCuCe/ZSM-5 catalyst prepared in example 1 with hydrogen in a fixed bed at a temperature of 350 ℃ and a hydrogen activation space velocity of 2500h -1 Activating time is 6h; then transferring the mixture into an intermittent kettle type reaction kettle under the protection of nitrogen, sealing, replacing air in the kettle with hydrogen, setting the reaction temperature of the reaction kettle to be 180 ℃, and filling the hydrogen to the set reaction pressure of 6MPa; when the reaction temperature reaches 180 ℃, stirring is started and timing is started, the stirring rotation speed is kept at 600r/min, after the reaction is carried out for 3 hours, a stirring and heating device is closed, a reaction kettle is cooled to room temperature and is depressurized to normal pressure, the mixture after the reaction is taken, the chromatographic analysis conversion rate is 99%, and the selectivity of hexamethylenediamine is 99.5%. And obtaining high-purity hexamethylenediamine after reduced pressure distillation and refining.
Example 4
A process for the preparation of hexamethylenediamine by hydrogenation of 6-aminocapronitrile comprising the steps of:
adding a 30% mass fraction of 6-aminocapronitrile ethanol solution into a batch kettle type reaction kettle, adding 20g (about 25 mL) of the reduced NiCuCe/ZSM-5 catalyst prepared in example 1 into the batch kettle type reaction kettle, sealing, replacing air in the kettle with hydrogen, heating and activating the catalyst, wherein the activating temperature of the catalyst is 350 ℃, and the space velocity of activated hydrogen is 2500h -1 The activation time was 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, after the reaction temperature reaches 180 ℃, stirring is started and timing is started, the stirring speed is kept at 600r/min, after the reaction is carried out for 4.5 hours, a stirring and heating device is closed, the reaction kettle is cooled to room temperature and is depressurized to normal pressure, the mixture after the reaction is taken, the conversion rate is 99% through chromatographic analysis, and the selectivity of hexamethylenediamine is 99.5%. And obtaining high-purity hexamethylenediamine after reduced pressure distillation and refining.
Example 5
A process for the preparation of hexamethylenediamine by hydrogenation of 6-aminocapronitrile comprising the steps of:
adding 5% 6-aminocapronitrile ethanol solutionIn a batch kettle, 20g (about 25 mL) of the NiCuLa/MCM-41 catalyst prepared in example 2 was heated and activated with hydrogen in a fixed bed at a temperature of 380 ℃ and a space velocity of the activated hydrogen of 2500h -1 Activating for 8h; then transferring the mixture into an intermittent kettle type reaction kettle under the protection of nitrogen, sealing, replacing air in the kettle with hydrogen, setting the reaction temperature of the reaction kettle to be 180 ℃, and filling the hydrogen to the set reaction pressure of 6MPa; when the reaction temperature reaches 180 ℃, stirring is started and timing is started, the rotating speed of stirring is kept at 600r/min, after the reaction is carried out for 1h, a stirring and heating device is closed, a reaction kettle is cooled to room temperature and is depressurized to normal pressure, the mixture after the reaction is taken, the chromatographic analysis conversion rate is 98%, and the selectivity of hexamethylenediamine is 99.5%. And obtaining high-purity hexamethylenediamine after reduced pressure distillation and refining.
Example 6
Adding 75% 6-aminocapronitrile ethanol solution into a batch kettle reaction kettle, heating and activating 20g (about 25 mL) of NiCuCe/ZSM-5 catalyst prepared in example 1 with hydrogen in a fixed bed at a temperature of 350 ℃ and a hydrogen activation space velocity of 2500h -1 Transferring the reaction kettle into an intermittent kettle type reaction kettle under the protection of nitrogen for 6 hours, sealing, replacing air in the kettle with hydrogen, setting the reaction temperature of the reaction kettle to be 180 ℃, and filling the hydrogen to the set reaction pressure of 6MPa; when the reaction temperature reaches 180 ℃, stirring is started and timing is started, the rotating speed of stirring is kept at 600r/min, after the reaction is carried out for 8 hours, a stirring and heating device is closed, a reaction kettle is cooled to room temperature and is depressurized to normal pressure, the mixture after the reaction is taken, the chromatographic analysis conversion rate is 95%, and the selectivity of hexamethylenediamine is 98.5%. And obtaining high-purity hexamethylenediamine after reduced pressure distillation and refining.
Example 7
20g (about 25 mL) of the NiCuCe/ZSM-5 catalyst prepared in example 1 was charged into a fixed bed reactor. The catalyst is used after hydrogen activation, the activation temperature is 320 ℃, the temperature programming is carried out for 1h, the activation temperature is reached from the room temperature, and the space velocity of the activated hydrogen is 2500h -1 Activated for 8h. After the catalyst is activated, the temperature of the bed layer is reduced to 180 ℃ of the reaction temperature, the pressure of the system is increased to 5MPa, and the mass fraction of the 6-aminocapronitrile is 20%Pumping the ethanol solution into a reaction system by a pump, wherein the airspeed is 1h -1 . The reaction mixture was taken and analyzed by chromatography to give a conversion of 97% and a hexamethylenediamine selectivity of 99.5%. And obtaining high-purity hexamethylenediamine after reduced pressure distillation and refining.
Comparative example 1
The process for preparing hexamethylenediamine by hydrogenation of 6-aminocapronitrile is the same as in example 3, except that the catalyst is a Raney nickel catalyst. The reaction mixture was taken and analyzed by chromatography to give a conversion of 92% and a hexamethylenediamine selectivity of 95.3%. And obtaining high-purity hexamethylenediamine after reduced pressure distillation and refining.
In conclusion, the porous molecular sieve supported copper-nickel-based catalyst prepared by adopting the coprecipitation method is characterized in that 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 rare earth metal improves the dispersity of copper and nickel, promotes the synergistic effect between copper and nickel, improves the hydrogenation effect of the whole catalyst, and is used for the reaction of synthesizing hexamethylenediamine by hydrogenating 6-aminocapronitrile, and the reaction conversion rate and the yield are high, and the purity of hexamethylenediamine is high. Compared with the preparation of Raney nickel catalyst, the catalyst prepared by the method has low cost, different chemical potentials of the components, more orderly mixing of the components in the solution in an ionic state under the action of the catalyst, simple production process, high process safety, low production cost, no three waste discharge and low equipment investment, and is suitable for large-scale production.
It should be noted that, when numerical ranges are referred to in the present invention, it should be understood that two endpoints of each numerical range and any numerical value between the two endpoints are optional, and because the adopted step method is the same as 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. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. The preparation method of the catalyst for synthesizing hexamethylenediamine is characterized by adopting a coprecipitation method to prepare a copper-nickel-based catalyst loaded by a porous molecular sieve, and comprises the following steps of:
s1, dissolving nickel nitrate, copper nitrate and rare earth metal nitrate in water to prepare a mixed solution;
s2, placing a molecular sieve in a reactor, adding water for mixing, then simultaneously dripping 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 dripping, then carrying out 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;
the content of copper oxide and nickel oxide in the catalyst is 15-55% of the total mass of the catalyst; the mass ratio of the copper oxide to the nickel oxide in the catalyst is 1:1-1.5;
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;
the porous molecular sieve is ZSM-5 or MCM-41, the aperture is 1-10nm, and the content of the porous molecular sieve is 25-65% of the total mass of the catalyst.
2. The method for preparing a catalyst for synthesizing hexamethylenediamine according to claim 1, wherein in S1, the concentration of metal ions in the mixed solution is 0.5-2.5mol/L.
3. The method for preparing the catalyst for synthesizing hexamethylenediamine according to claim 1, wherein in S2, the molar ratio of the precipitant to the metal ions in the mixed solution is 1-3:1, and the precipitant is aqueous ammonia, sodium carbonate solution or sodium bicarbonate solution having ph=11.
4. The method for preparing a catalyst for synthesizing hexamethylenediamine according to claim 1, wherein in S2, the temperature of the reaction is 35-55 ℃; 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.
5. A catalyst prepared by the method for preparing a catalyst for synthesizing hexamethylenediamine according to any one of claims 1 to 4.
6. The use of the catalyst according to claim 5 for synthesizing hexamethylenediamine by hydrogenating 6-aminocapronitrile, wherein the catalyst is used in an amount of 1-5% by mass of the total mass of the reaction raw materials.
7. The use of the catalyst according to claim 6 in the hydrogenation synthesis of hexamethylenediamine from 6-aminocapronitrile, wherein the synthesis reaction is a batch-tank reaction or a fixed-bed reaction in which the activation temperature is 300-450 ℃ and the hydrogen gas space velocity is 2000-3500h before the catalyst is used -1 The activation time is 5-10h; the temperature of the batch kettle 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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